JP2007056274A - Resin film for metal sheet laminate, method for production thereof, resin laminated metal sheet, and method for production thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin film for a metal sheet lamination which endures severe forming owing to excellent formability and impact resistance, and also to excellent adhesion after forming and heating, further gives stable performance independent of forming conditions, and also provide a laminated metal sheet and a method for manufacturing the same. <P>SOLUTION: The resin film for a metal sheet laminate has a mixed resin in which a granular resin mainly existing in a state of grains having 0.1 to 5 μm in diameter is dispersed in a polyester resin in an amount of 3 to 30 wt.% in the total resin. The granular resin is a modified polyolefin containing a functional groups derived from carboxylic acid in a range from 2 to 20 wt.% as carboxylic acid. The modified polyolefin resin is in granular particles of a particle size of 0.1 to 5 μm and the volume fraction of the particles is 3 to 25 vol.% in the mixed resin. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is excellent in workability and impact resistance, and also excellent in adhesion to the base metal after processing and after heating, so that a metal plate laminating resin film that can withstand severe molding processing, its manufacturing method, The present invention relates to a laminated metal plate and a manufacturing method thereof.

  In addition, the present invention relates to a resin film for laminating a metal plate that is excellent in flavor properties, a production method thereof, a laminated metal plate, and a production method thereof.

  In addition, the present invention relates to a resin film for laminating a metal plate that is excellent in retort processing properties, particularly capable of preventing white turbidity of a film generated during retort processing, a manufacturing method thereof, a laminated metal plate, and a manufacturing method thereof.

  Conventionally, materials for metal cans, such as thin-walled deep-drawn cans and squeezed iron cans (DI cans), which are forced to be severely molded, have a reduced taste and flavor due to metal elution from the metal plate, and further the alteration of the contents. In order to prevent generation and the like, a resin layer provided on the inner surface side of the can is generally used. As a can having a resin layer provided on the inner surface side of such a can and a resin-coated metal plate capable of forming such a can, a polyester-based substitute for an epoxy-based coating layer that has recently been pointed out to be dangerous for environmental hormones A metal plate laminated with a resin is used.

  The polyester resin used in such applications is required to have the following performance. In other words, it has excellent adhesion to the metal plate, there is no deformation such as elongation or compression of the film due to the molding process during can making, no deterioration of the film due to friction during can forming, and no decrease in adhesion, drying after can making The polyester resin film laminated by heating such as printing, baking, retort sterilization, etc. will be crystallized or deteriorated, and will not cause film peeling, shrinkage, cracks, pinholes, etc. May not occur or peel off, may not corrode or peel off when in contact with various contents, and the film may not become cloudy. Furthermore, it is also required that the scent component of the contents of the can be adsorbed on the polyester film, and that the flavor of the contents is not impaired by the elution component and odor of the polyester film (hereinafter referred to as flavor properties).

  For example, Patent Document 1 proposes a metal plate coated with a polyethylene terephthalate resin from the viewpoint of moldability, heat resistance, corrosion resistance, flavor properties, and the like, and Patent Document 2 discloses a polybutylene terephthalate resin. A metal plate coated with is proposed. Furthermore, the coating resin used for such a metal can material is required to have excellent formability that can follow the drawing and ironing process, and has excellent adhesion so as not to peel from the steel sheet, and a punching can. At the same time, since excellent impact resistance that can withstand impact during canning process and transportation is required, Patent Document 3 and Patent Document 4 include the food hygiene property inherent in the polyethylene terephthalate resin film, In addition to flavor properties, a production method has been proposed in which excellent crystal formability, adhesion, and impact resistance are compatible by controlling the crystal orientation of the film with a lamination technique or the like. Such a technique was applicable in the present required level of moldability, adhesion and impact resistance.

  However, in this field, the thickness of the material has been decreasing year by year to reduce the weight of the material. This trend is expected to continue in the future, but the current polyethylene terephthalate resin production method described above requires more stringent processing. When it is used, it is difficult to achieve both workability and impact resistance. This is because processability and impact resistance tend to conflict with each other in performance that greatly depends on the crystal orientation (plane orientation) of the resin layer. That is, when the crystal orientation component increases in the resin layer, plastic deformation is hindered in the crystal part, and workability is lowered. For this reason, from the viewpoint of workability, the smaller the amount of oriented crystal, the better. However, when subjected to impact, this crystal portion acts as a site that stops the progress of cracking, so from the viewpoint of impact resistance, the amount of oriented crystal. The more is better. In this way, workability and impact resistance are designed by adjusting the amount of oriented crystals so that both characteristics are acceptable. However, the current required performance is the limit in the range where both characteristics are compatible, and the development of a new highly workable film that can cope with future increases in the degree of processing, and the film laminated metal plate covering it is expected. It was.

  In response to such needs, studies have been vigorously conducted on the technology of achieving both high workability and impact resistance by mixing a polyolefin resin with a polyester resin. Patent Documents 5 and 6 disclose a technique of laminating a film made of a composition of a saturated polyester resin and an ionomer resin on a metal plate, and show that impact resistance can be maintained even in an amorphous state. However, the impact resistance obtained by simply adding an ionomer is not sufficient, and conversely, since the orientation of the polyester resin is actually hindered by the addition of the ionomer, the mechanical strength inherent to the polyester resin is reduced, and the resin at the time of molding. There is a problem that it is easy to break. Moreover, it is inferior also to adhesiveness with the base metal after a process and after a heating.

  Furthermore, Patent Document 7 and Patent Document 8 show that a ternary composition of a polyester resin, a polyester elastomer, and an ionomer resin can be laminated on a metal plate to improve impact resistance. However, the effect of improving the impact resistance of the polyester resin is negligible due to its low ability to relieve the impact stress of the polyester elastomer. It also has poor adhesion.

  On the other hand, in Patent Document 9, a rubber-like elastic body encapsulated with a vinyl polymer having a polar group in a polyester resin by mixing a vinyl polymer having a polar group with a rubber-like elastic resin in a polyester resin. A technique for finely dispersing a resin is disclosed. Impact resistance was improved by such fine dispersion of the elastic resin, and the level of moldability and impact resistance became high. However, it is difficult to manage the process for producing such a capsule state, and the dispersion state of the elastic resin changes greatly depending on the molding conditions of the resin and is not stable, so that the performance as a resulting resin film is not always constant. There was a point. It has been found that when the dispersion state deviates from the optimum condition, the performance is greatly deteriorated. In fact, even if a resin having such a composition is produced, a part with low resin performance is produced, and the total is obtained. Performance such as moldability and impact resistance is insufficient. In addition, there are problems such as a decrease in adhesion to the base metal due to processing and impact, and a decrease in adhesion after heating.

  Furthermore, in Patent Document 10, the decomposition of the vinyl polymer is suppressed by adding an appropriate amount of an antioxidant (radical inhibitor) to the mixed resin in which the vinyl polymer having a polar group is finely dispersed in the polyester resin. Techniques for making them disclosed are disclosed. However, in a mixture of a specific vinyl polymer and a polyester resin, when the polymerization catalyst for the polyester resin and the antioxidant coexist, the resin tends to deteriorate. In particular, the polyester resin is deteriorated, and the performance such as impact resistance and flavor is lowered.

  Furthermore, Patent Document 11 discloses a technique for improving workability, impact resistance, and adhesion by coating a resin layer in which a fine ionomer resin is present as a dispersed phase in a polyester resin. The composition of the modified polyolefin resin to be dispersed and the composition of the polyester resin were not appropriate, and the performance was insufficient.

  In addition, in a can using a metal plate laminated with such a film, there is a problem that the film becomes cloudy after retort treatment and the appearance deteriorates, particularly in a can lid or can bottom where retort vapor directly contacts, The prior art does not consider preventing such cloudiness.

The prior art document information will be described below. Note that Patent Documents 12 to 19 are described in the section of [Best Mode for Carrying Out the Invention] for convenience of description.
JP 59-2322852 Japanese Patent Laid-Open No. 1-180336 JP-A-5-269920 JP-A-6-320669 JP-A-7-195617 JP-A-7-195618 Japanese Patent Laid-Open No. 7-290643 Japanese Patent Laid-Open No. 7-290644 WO99 / 27026 pamphlet JP 2001-172481 A JP 2001-353814 A Japanese Patent Laid-Open No. 5-222357 JP-A-5-1164 JP 11-48431 A JP-A-11-138702 Japanese Patent Publication No.54-22234 Japanese Patent Publication No. 60-12233 Japanese Patent Publication No. 63-13829 JP-A 61-149341

  In order to solve such problems, the present invention provides a solution to the problem, and is excellent in workability and impact resistance, and also excellent in adhesion after heating and after processing. In addition, the present invention provides a resin film for laminating metal plates, a method for producing the same, a laminated metal plate, and a method for producing the same, which can stably obtain performance regardless of molding conditions.

  Moreover, this invention provides the resin film for metal plate lamination which is excellent also in flavor property, its manufacturing method, a laminated metal plate, and its manufacturing method.

  The present invention also provides a resin film for laminating a metal plate that is excellent in retort processing properties, particularly capable of preventing white turbidity of a film that occurs during retorting, a method for producing the same, a laminated metal plate, and a method for producing the same.

  The present inventors have studied the structure of a resin layer that can withstand more severe processing and retain performance such as impact resistance and adhesion without losing the original processability and flavor properties of the polyester resin. . Furthermore, as a result of searching for a resin composition whose structure can be stably obtained regardless of molding conditions, in a metal plate coated with a resin film made of a mixed resin in which a granular modified polyolefin resin having a specific composition is dispersed in a polyester resin It has been found that remarkably high workability, impact resistance and flavor properties are obtained, and that the adhesiveness after processing and heating is also excellent. Moreover, since the resin structure can be stably obtained regardless of the molding conditions, high performance can be stably obtained. Furthermore, it was confirmed that the resin composition has sufficient characteristics such as corrosion resistance.

  The optimum resin structure of the mixed resin layer is obtained when a granular modified polyolefin resin containing a specific amount of a functional group derived from carboxylic acid is dispersed in a polyester resin. This is because the modified polyolefin resin having such a functional group composition is most stably dispersed in the polyester resin and the mechanical performance of the modified polyolefin resin itself is optimal, so that the maximum workability and impact resistance are achieved. It is obtained.

  The following mechanism is presumed as the reason why both workability and impact resistance can be achieved. When a breaking force is applied to the resin due to severe processing or impact, crazes and cracks occur in the polyester resin, which grows and breaks. However, a granular modified polyolefin resin with an appropriate composition and size is contained in the polyester resin. If dispersed, the development of such crazes and cracks is suppressed by the stress relaxation of the modified polyolefin resin, and it is possible to suppress breakage. Furthermore, the effect that the plastic deformation of the polyester resin is promoted around the contact between the modified polyolefin resin and the polyester resin appears, and the stress concentration leading to the breakage is alleviated, and the resin is hardly broken.

  A resin film in which a modified polyolefin resin containing such a carboxylic acid is mixed with a polyester resin has high adhesion to the base metal compared to a normal polyester resin, but is insufficient when subjected to more severe processing. There is a possibility. In addition, a film having such a resin composition exhibits a high degree of workability and impact resistance, and a sufficient flavor for normal use. However, depending on the application, it is very sensitive to changes in flavor in recent years. It is true that there are many new people and there are very strict requirements. In response to such a requirement, the polyester resin in which the modified olefin is dispersed contains an olefin component, so that the flavor property may be insufficient.

  Thus, as a result of intensive studies, it was found that the adhesiveness after processing and after heating was dramatically improved by using a layer of a modified polyolefin resin containing a carboxylic acid as a layer in contact with a metal plate. Furthermore, since this modified polyolefin resin layer is also excellent in adhesiveness with the mixed resin layer, there is no delamination and the entire adhesiveness can be maintained. Moreover, it turned out that flavor property can be improved more than a request | requirement level by superimposing the polyester resin layer which does not contain polyolefin resin on a modified olefin dispersion | distribution polyester layer.

  The present invention has been made based on the above-mentioned idea and knowledge, and the gist thereof is as follows.

  (1) From a mixed resin in which a granular resin mainly present in a granular state having a particle diameter of 0.1 to 5 μm is dispersed in a thermoplastic polyester resin in a range of 3 to 30% by weight in the total resin. The granular resin is a modified polyolefin resin containing a functional group derived from a carboxylic acid in an amount of 2 to 20% by weight in terms of a weight ratio in terms of carboxylic acid.

  (2) In the modified polyolefin resin, the amount of the modified polyolefin resin present in the film in a granular state with a particle diameter of 0.1 to 5 μm is in the range of 3 to 25 vol% in terms of the volume fraction in the mixed resin. The resin film for metal plate lamination according to (1), which is characterized in that

  (3) The thermoplastic polyester resin is a polyester mainly composed of polyethylene terephthalate and / or isophthalic acid-copolymerized polyethylene terephthalate, for metal plate lamination according to (1) or (2) above Resin film.

  (4) Any of (1) to (3) above, wherein the ratio of terephthalic acid and isophthalic acid of the dicarboxylic acid component constituting the thermoplastic polyester resin is 97: 3 to 85:15 in molar ratio A resin film for laminating metal plates according to claim 1.

  (5) As for the main monomer component which comprises the said thermoplastic polyester resin, dicarboxylic acid is a terephthalic acid, a diol component is ethylene glycol and 1, 4- butanediol, The ratio is 20: 80-80: The metal plate laminating resin film according to any one of the above (1) to (4), which is 20.

  (6) The ratio X / Y between the polyester polymerization catalyst amount X and the antioxidant amount Y in the mixed resin is 0.2 or more by weight, and any one of the above (1) to (5) 2. A resin film for laminating a metal plate.

  (7) Antioxidant content in the said mixed resin is 500 ppm or less, The resin film for metal plate lamination in any one of said (1)-(6) characterized by the above-mentioned.

  (8) The resin film for metal plate lamination according to any one of (1) to (7), wherein the resin film contains 5 to 40% by weight of a pigment in a weight ratio.

  (9) The resin film for laminating a metal plate according to any one of (1) to (8), wherein the resin film has a thickness of 10 to 50 μm.

  (10) A polyester resin layer R0 layer mainly composed of a resin layer R1 layer made of the mixed resin according to any one of (1) to (8) and polyethylene terephthalate copolymerized with polyethylene terephthalate and / or isophthalic acid. A metal plate laminating resin film, wherein the R0 layer is the outermost layer when laminated on a metal plate.

  (11) The thickness of the R1 layer is 10 to 50 μm, the thickness of the R0 layer is 1 to 10 μm, and the thickness ratio R1 / R0 between the R1 layer and the R0 layer is R1 / R0 = 2/1 to 10 The resin film for laminating metal plates according to (10), wherein the resin film is / 1.

  (12) The resin layer R1 layer composed of the mixed resin according to any one of (1) to (8) and the resin layer R2 layer mainly composed of a modified polyolefin resin having a functional group derived from carboxylic acid are laminated. A resin film for laminating a metal plate, wherein the R2 layer is designed to be in contact with the metal plate when laminated on the metal plate.

  (13) The thickness of the R1 layer is 10 to 50 μm, the thickness of the R2 layer is 1 to 10 μm, and the thickness ratio R1 / R2 between the R1 layer and the R2 layer is R1 / R2 = 1/1 to 20 / The metal plate laminating resin film as described in (12) above, which is 1.

  (14) A main skeleton mainly composed of polyethylene terephthalate copolymerized with polyethylene terephthalate and / or isophthalic acid on one surface of the resin layer R1 layer made of the mixed resin according to any one of (1) to (8). R0 layer in which a polyester resin layer R0 layer is laminated and a resin layer R2 layer mainly composed of a modified polyolefin resin having a functional group derived from carboxylic acid is laminated on the other surface of the R1 layer. A resin film for laminating a metal plate, which is a film having a three-layer structure of / R1 layer / R2 layer and designed so that the R0 layer becomes an outermost layer when laminated on a metal plate.

  (15) The film thickness of the R1 layer is 10 to 50 μm, the film thickness of the R0 layer is 1 to 10 μm, the film thickness of the R2 layer is 1 to 10 μm, and the thickness ratio R1 / R0 between the R1 layer and the R0 layer is R1 / R0 = 2/1 to 10/1 and the thickness ratio R1 / R2 to the R2 layer is R1 / R2 = 1/1 to 20/1, as described in (14) above Resin film for laminating metal plates.

  (16) Any one of the above (12) to (15), wherein the modified polyolefin resin of the R2 layer contains a functional group derived from carboxylic acid in a weight ratio of 2 to 20% by weight in terms of carboxylic acid. 2. A resin film for laminating a metal plate.

  (17) The resin film for metal plate lamination according to any one of (10) to (16), wherein the resin film contains 5 to 40% by weight of a pigment in a weight ratio.

  (18) The thermoplastic polyester according to any one of (1) to (8) as a raw material resin in producing the resin film for metal plate lamination according to any one of (1) to (9). A resin for laminating metal plates, characterized in that a mixed resin in which a granular modified polyolefin resin having a particle size of 0.1 to 5 μm is dispersed in the resin is inserted into an extruder and melted, and extruded from a T-die to form a film. A method for producing a film.

  (19) In producing the resin film for metal plate lamination according to (10), (11), or (17), any of the above (1) to (8) is used as a resin as a raw material for the R1 layer. A resin, in which a granular modified polyolefin resin having a particle size of 0.1 to 5 μm previously dispersed in the thermoplastic polyester resin described above is inserted into an extruder and melted, and at the same time, the resin used as the raw material of the R0 layer A polyester resin having polyethylene terephthalate and / or polyethylene terephthalate copolymerized with isophthalic acid as a main basic skeleton is inserted into another extruder and melted, and the molten resin is extruded from one T die, and R1 layer / R0 A method for producing a resin film for laminating metal plates, comprising forming a film having a two-layer structure of layers.

  (20) In manufacturing the resin film for metal plate lamination according to (12), (13), (16), or (17), as the resin that is a raw material of the R1 layer, (1) to (1) 8) A mixed resin in which a granular modified polyolefin resin having a particle size of 0.1 to 5 μm is dispersed in advance in the thermoplastic polyester resin described in any of the above items is inserted into an extruder and melted. As a raw material resin, a resin having a modified polyolefin resin having a functional group derived from carboxylic acid as a main component is inserted into another extruder and melted, and the molten resin is extruded from one T die, and the R1 layer A method for producing a resin film for laminating metal plates, comprising forming a film having a two-layer structure of / R2.

  (21) In manufacturing the resin film for metal plate lamination according to the above (14) to (17), the resin as a raw material for the R1 layer is described in any one of the above (1) to (8). Polyethylene terephthalate is used as a raw material for the R0 layer by inserting a molten resin in which a granular modified polyolefin resin having a particle size of 0.1 to 5 μm in a thermoplastic polyester resin is dispersed in advance into an extruder and melting it. And / or polyester resin mainly composed of polyethylene terephthalate copolymerized with isophthalic acid, and a modified polyolefin resin having a functional group derived from carboxylic acid as a main component as a raw material for the R2 layer. Each of the resins is inserted into an extruder different from the extruder and melted to obtain one molten resin. T extruding from the die, R0 layer / R1 layer / R2 layer metal sheet manufacturing method of laminating a resin film, which comprises forming a film of three-layer structure.

  (22) The resin film described in any one of (1) to (17) or the method described in any one of (18) to (21) is manufactured on at least one surface of a metal plate. A laminated metal plate characterized by covering with a resin film.

(23) a metal plate, a metal layer of chromium coating weight 50-200 mg / ^{m 2} on the surface, that the amount of deposition of metallic chromium conversion is electrolytic chromate treated steel sheet having a chromium oxide layer of 3 to 30 mg / ^{m 2} The laminated metal plate according to (22), characterized in that:

  (24) The laminated metal plate according to (22) or (23), wherein a plane orientation coefficient in a direction parallel to the film surface of the resin film is less than 0.010.

  (25) The resin film is coated by an extrusion laminating method in which the mixed resin described in any one of (1) to (8) is extruded from a T die and directly coated on the surface of a metal plate. The laminated metal plate according to any one of (22) to (24), wherein:

  (26) The resin film mainly includes a resin layer (R1 layer) made of the mixed resin described in any one of (1) to (8) and polyethylene terephthalate copolymerized with polyethylene terephthalate and / or isophthalic acid. Two types of resins consisting of a resin layer (R0 layer) made of polyester resin as a basic skeleton are coated by a two-layer extrusion lamination method in which a metal plate surface is directly extruded from one T-die at the same time. The laminated metal plate according to any one of (22) to (24), wherein:

  (27) The resin film mainly includes a resin layer (R1 layer) made of the mixed resin described in any one of (1) to (8) and a modified polyolefin resin having a functional group derived from carboxylic acid. Two types of resin comprising resin layer R2 as a component are coated by a two-layer extrusion laminating method in which two types of resin are simultaneously extruded from one T-die and directly coated on the surface of a metal plate. The laminated metal plate according to any one of 22) to (24).

  (28) The resin film includes a resin layer (R0 layer) made of a polyester resin mainly composed of polyethylene terephthalate copolymerized with polyethylene terephthalate and / or isophthalic acid, and any one of the above (1) to (8) 3 types of resin consisting of a resin layer (R1 layer) composed of the mixed resin described in 1) and a resin layer R2 layer mainly composed of a modified polyolefin resin having a functional group derived from carboxylic acid is used as one T die. The laminated metal plate according to any one of the above (22) to (24), which is coated by a three-layer extrusion laminating method in which the metal plate is directly extruded and coated on the surface of the metal plate.

  (29) In manufacturing the laminated metal plate according to any one of (22) to (28), the melting point of the polyester resin in the mixed resin described in any one of (1) to (8) is −70. A method for producing a laminated metal plate, comprising laminating a resin film on a metal plate heated to a temperature in the range of from ° C to the melting point + 30 ° C.

  (30) In manufacturing the laminated metal plate according to (25), the mixed resin is heated and melted in the range of the melting point of the polyester resin in the mixed resin + 10 ° C. to the melting point + 50 ° C. A method for producing a laminated metal plate, wherein the laminate is extruded directly onto the surface of the laminate.

  (31) As a raw material resin, a granular modified polyolefin resin having a particle diameter of 0.1 to 5 μm is dispersed in advance in the thermoplastic polyester resin described in any of (1) to (8) above. The method for producing a laminated metal plate according to (30), wherein the mixed resin is inserted into an extruder and melted, and then extruded and laminated directly on the surface of the metal plate.

  (32) In manufacturing the laminated metal sheet according to (26), after heating and melting the R1 layer and the R0 layer in the range of the melting point of the polyester resin of the R1 layer + 10 ° C to the melting point + 50 ° C, A method for producing a laminated metal plate, comprising: laminating two layers on a surface of a metal plate.

  (33) In the thermoplastic polyester resin described in any one of (1) to (8) above, a granular modified polyolefin resin having a particle diameter of 0.1 to 5 μm is preliminarily used as a raw material for the R1 layer. The dispersed mixed resin is inserted into an extruder, and at the same time, a resin made of a polyester resin mainly composed of polyethylene terephthalate and polyethylene terephthalate copolymerized with polyethylene terephthalate and / or isophthalic acid is used as another raw material for the R0 layer. The method for producing a laminated metal plate according to the above (32), which is inserted into a machine, melted, and then extruded and laminated directly on the surface of the metal plate.

  (34) In manufacturing the laminated metal plate according to (27), the R1 layer and the R2 layer are heated in the range of the melting point of the polyester resin of the R1 layer + 10 ° C. to the melting point + 50 ° C. and melted, A method for producing a laminated metal plate, comprising: laminating two layers on a surface of a metal plate.

  (35) In the thermoplastic polyester resin described in any one of (1) to (8) above, a granular modified polyolefin resin having a particle diameter of 0.1 to 5 μm is preliminarily used as a raw material for the R1 layer. The dispersed mixed resin is inserted into an extruder, and at the same time, a resin mainly composed of a modified polyolefin resin having a functional group derived from carboxylic acid is inserted into another extruder as a raw material for the R2 layer, The method for producing a laminated metal plate according to the above (34), wherein the laminate is melted and then extruded and laminated directly on the surface of the metal plate.

  (36) In manufacturing the laminated metal plate according to (28), the R1 layer, the R2 layer, and the R0 layer are heated and melted in the range of the melting point of the polyester resin of the R1 layer + 10 ° C to the melting point + 50 ° C. And then laminating and extruding three layers on the surface of the metal plate.

  (37) In the thermoplastic polyester resin described in any one of (1) to (8) above, a granular modified polyolefin resin having a particle diameter of 0.1 to 5 μm is preliminarily used as a resin that is a raw material for the R1 layer. The dispersed mixed resin is inserted into an extruder and melted, and at the same time, a resin comprising a polyester resin mainly composed of polyethylene terephthalate copolymerized with polyethylene terephthalate and / or isophthalic acid is used as a raw material for the R0 layer. In addition, as a raw material for the R2 layer, a resin mainly composed of a modified polyolefin resin having a functional group derived from a carboxylic acid is inserted into an extruder different from the above-mentioned extruder, and then melted. And then laminating by directly extruding to the surface of the metal plate and laminating. Method of manufacturing a door metal plate.

  ADVANTAGE OF THE INVENTION According to this invention, the resin film for metal plate lamination which was excellent in workability, impact resistance, adhesiveness, and also the flavor property and retort processing property, a laminated metal plate, and its manufacturing method are obtained. The laminated metal plate of the present invention can be suitably used for two-piece metal can applications produced by drawing or ironing. Further, it can be preferably used as a lid part of a two-piece can, or a body, lid, or bottom metal plate of a three-piece can.

  In addition, the laminated metal plate of the present invention is suitable as a material for use in a thin-walled deep-drawn can that is required to be severely formed because the thickness of the material is reduced and the thickness is reduced.

  The laminated metal plate of the present invention is suitable for use in applications where white turbidity is a problem, such as a cover for two-piece cans and three-piece cans, because the film does not have white turbidity during retort processing.

  The resin film for laminating a metal plate of the present invention, a production method thereof, a laminated metal plate and a production method thereof will be described below.

  In the resin film of the present invention, a granular resin mainly present in a granular state with a particle diameter of 0.1 to 5 μm is dispersed in a thermoplastic polyester resin in a range of 3 to 30% by weight in the total resin. The granular resin is a modified polyolefin resin having a functional group derived from carboxylic acid.

  That is, the resin film of the present invention contains a thermoplastic polyester resin as a main component. As the thermoplastic polyester resin, those obtained by arbitrarily copolymerizing various aromatic dicarboxylic acids and aliphatic dicarboxylic acids as the acid component, and arbitrarily copolymerizing various aliphatic diols and aromatic diols as the glycol component are used.

  Specific examples of the acid component include terephthalic acid, phthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid. 4,4'-biphenyldicarboxylic acid, diphenic acid, diphenyl ether carboxylic acid, 5-sulfoisophthalic acid, diphenoxyethanedicarboxylic acid, adipic acid, oxalic acid, malonic acid, succinic acid, malic acid, citric acid, glutaric acid, Dimer acid, pimelic acid, speric acid, azelaic acid, sepacic acid, dodecadioic acid, trans-1,4-cyclohexanedicarboxylic acid and the like are used. In particular, those containing terephthalic acid and / or isophthalic acid as the main component are preferable from the viewpoint of balance between mechanical properties and flavor properties.

  On the other hand, as the glycol component, specifically, ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, neopentyl glycol, pentamethylene glycol, hexamethylene glycol , Diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, trans-1,4-cyclohexanedimethanol, bisphenols, p-xylene glycol, cis-1,4-cyclohexanedimethanol, hydroquinone, 2,2-bis ( 4-β-hydroxyethoxyphenyl) propane, hydrogenated bisphenol A and the like are used. In particular, those based on ethylene glycol and / or 1,4-butanediol are preferred from the standpoint of balance between mechanical properties and flavor properties.

  That is, terephthalic acid and ethylene glycol are the main components, and / or terephthalic acid and isophthalic acid and ethylene glycol are the main components, and / or terephthalic acid and ethylene glycol and 1,4-butanediol are the main components. Is particularly suitable from the viewpoint of the balance between mechanical properties and flavor properties in a mixed resin state.

  As the thermoplastic polyester resin, a polyester resin having polyethylene terephthalate and / or isophthalic acid copolymerized polyethylene terephthalate as a main basic skeleton is preferable. Polyester resin comprising polyethylene terephthalate and / or isophthalic acid copolymer polyethylene terephthalate as the main basic skeleton means a part of the polyester resin skeleton containing only ethylene glycol and terephthalic acid as a structural unit and / or ethylene glycol, terephthalic acid and isophthalic acid The total of the parts having the structural units occupy 90% by weight or more, and the acid component may optionally copolymerize various aromatic dicarboxylic acids and aliphatic dicarboxylic acids at other sites.

  Further, a small amount of a structural unit derived from a polyfunctional compound such as trimesic acid, pyromellitic acid, trimethylol ethane, trimethylol propane, trimethylol methane, pentaerythritol, or the like, as long as the object of the invention is not impaired. It may be included in the following amounts.

  The polyester resin of the present invention preferably has a diethylene glycol content of 1.5% by weight or less, more preferably 0.9% by weight or less. When the polyester contains a large amount of diethylene glycol, the deterioration of the polymer progresses due to heat treatment such as drying during printing and printing, and cracks and pinholes occur, resulting in poor impact resistance and flavor. There is.

  Moreover, it is preferable that the acetaldehyde content in resin is 10 ppm or less from the point of flavor property, More preferably, it is 7 ppm or less. If the acetaldehyde content exceeds this range, particularly 10 ppm, the flavor properties may be inferior. The method for setting the acetaldehyde content to 10 ppm or less is not particularly limited. For example, in order to remove acetaldehyde generated by thermal decomposition when a polyester resin is produced by polycondensation reaction or the like, the resin was obtained by a method of heat-treating the resin at a temperature below the melting point of the polyester under reduced pressure or in an inert gas atmosphere. Examples include a method of forming a polyester resin into a film, and a method of using a polyester resin obtained by solid-phase polymerization at a temperature of 150 ° C. or higher and a melting point or lower in a reduced pressure or inert gas atmosphere is preferable.

  Further, the polyester resin of the present invention preferably has fewer oligomers composed of a cyclic trimer or the like in the resin from the viewpoint of flavor. In particular, the content of the cyclic trimer is preferably 0.9% by weight or less, and more preferably 0.7% by weight or less. If the oligomer content in the resin exceeds this range, particularly 0.9% by weight, the flavor properties may be inferior. The method for setting the oligomer content to 0.9% by weight or less is not particularly limited, but can be achieved by adopting a method similar to the method for reducing the acetaldehyde content described above.

The intrinsic viscosity of the polyester resin used in the present invention is 0.3 to 2.0 dl / g, more preferably 0.3 to 1.5 dl / g, and still more preferably 0.5 to 1.0 dl / g. If it exceeds 2.0 dl / g, the viscosity is so high that mixing with the modified polyolefin resin becomes extremely difficult, and the modified polyolefin resin is not uniformly dispersed. As a result, the mechanical strength and impact resistance of the polyester resin may be lowered. On the other hand, when the intrinsic viscosity is less than 0.3 dl / g, since the viscosity is low, the moldability becomes poor, and it may be difficult to produce a uniform film. The intrinsic viscosity is measured by the method shown in JIS K7367-5, and is measured at a concentration of 0.005 g / ml in o-chlorophenol at 25 ° C. The intrinsic viscosity = (T−T ₀ ) / It is determined by the expression _(T 0 * c). In the formula, c represents the concentration of the resin per 100 ml of the solution expressed in grams, and T ₀ and T represent the flow time of the solvent and the resin solution in the capillary viscometer, respectively.

  Furthermore, it is desirable that the polyester resin used in the present invention has a glass transition temperature (Tg) of 50 to 120 ° C, more preferably 60 to 100 ° C. When the glass transition temperature is less than 50 ° C, the heat resistance of the polyester resin is inferior, so that scratches and the like are liable to occur due to the temperature rise during molding. On the other hand, when the glass transition temperature exceeds 120 ° C, the workability is reversed. May be inferior. The low-temperature crystallization temperature (Tc) is usually 130 to 210 ° C, preferably 140 to 200 ° C, and the melting point (Tm) is usually 210 to 265 ° C, preferably 220 to 260 ° C. . When the low temperature crystallization temperature is less than 130 ° C., crystallization is likely to occur, so that crystallization occurs during retort sterilization treatment (high temperature and high humidity treatment at about 120 ° C., also referred to as “retort treatment” in this specification). Cracks and peeling easily occur, while those exceeding 210 ° C. may be inferior in mechanical strength such as processability and impact resistance of polyester. If the melting point is less than 210 ° C, the resin deteriorates due to heat during molding, and cracks and pinholes are likely to occur. On the other hand, those that exceed 265 ° C are crystallized by heat treatment such as drying and printing baking during molding. As a result, cracks and pinholes are likely to occur. The glass transition temperature, the low temperature crystallization temperature, and the crystal melting temperature are obtained by measuring the endothermic peak temperature at the time of temperature rise using a differential scanning calorimeter (DSC). The sample amount is 10 mg, the temperature rise rate is 10 ° C./min. It is a value measured under conditions.

  In the present invention, in the dicarboxylic acid component constituting the polyester resin, the ratio of the total terephthalic acid amount and the total isophthalic acid amount is specified as 97: 3 to 85:15 in terms of molar ratio. In the mixed resin in the present invention, the modified polyolefin in the resin prevents the crystallization of the polyester resin, and the adhesion and corrosion resistance due to processing and heating are less likely to occur. This ratio spreads to the terephthalic acid rich side, and even if a homoethylene terephthalate resin containing no isophthalic acid is used as a polyester resin, it can be used as a normal can material if it contains the modified polyolefin resin of the present invention. is there. Furthermore, if the isophthalic acid ratio is 3 mol%, the adhesion after processing and heating is drastically improved. If the ratio of the total amount of terephthalic acid to the total amount of isophthalic acid is more than 85:15, the melting point is lowered and the heat resistance during molding may be inferior.

  In particular, in applications where retorting is performed, in the main monomer component constituting the thermoplastic polyester resin, the dicarboxylic acid is terephthalic acid, the diol component is ethylene glycol and 1,4-butanediol, and the ratio of both (diol The most suitable component is a ratio of ethylene glycol amount and 1,4 butanediol amount) of 20:80 to 80:20 in terms of molar ratio. Furthermore, the range of 60:40 to 30:70 is most appropriate. In the polyester resin containing the polyolefin resin as described above, the modified polyolefin resin in the resin hinders the crystallization of the polyester resin. Therefore, particularly in the retort treatment, the strength of the polyester resin is insufficient and the cohesive failure is likely to occur. was there. In response to such a problem, by mixing polybutylene terephthalate, which has a particularly high crystallization rate, with polyethylene terephthalate in a predetermined ratio, crystallization of the polyester resin is accelerated, and cohesive failure is less likely to occur even in retort processing. Such an effect is particularly remarkable in the prevention of a phenomenon in which water vapor that has entered the film during retort treatment causes the film to cohesively break and cause the film to become cloudy in the cover material laminated with the film, and the polyester resin having the above composition is used. By doing so, such a problem can be solved. When the ratio of polyethylene terephthalate to polybutylene terephthalate is higher than 80:20 in terms of molar ratio, the crystallization speed is not sufficiently increased and the above-mentioned effect cannot be expected. On the other hand, if the amount of polybutylene terephthalate is higher than 20:80, the melting point is low and the heat resistance is poor.

  A modified polyolefin resin having a functional group derived from a carboxylic acid mixed in a polyester resin improves impact resistance and does not adversely affect other properties such as processability and heat resistance. It is necessary that the particle diameter is mainly present in a state of 0.1 to 5 μm in the equivalent sphere conversion meter. In this case, “mainly present” means that at least 30% by weight in the total modified polyolefin resin is present in an equivalent sphere equivalent diameter of 0.1 to 5 μm. Further, the weight ratio of the modified polyolefin resin in all resins needs to be in the range of 3 to 30% by weight.

  When the modified polyolefin resin is dispersed in the polyester resin, a wide dispersion occurs from a very fine particle having a particle size of 0.1 μm or less to a large particle having a particle size exceeding 5 μm. It does not affect the physical properties at all, and on the other hand, it does not improve or rather deteriorates the physical properties such as the processability of the mixed resin even for particles having a particle diameter exceeding 5 μm. Therefore, at least 30% by weight in the total modified polyolefin resin The thing needs to be in the range of 0.1 to 5 μm in terms of equivalent sphere diameter. From the viewpoint of suppressing deterioration of physical properties, the weight ratio of particles having a particle diameter exceeding 5 μm is preferably 1% or less. Further, when the weight ratio of the modified polyolefin resin to be mixed in the total resin is less than 3% by weight, the impact resistance is insufficient to improve, and when it exceeds 30% by weight, the performance such as workability and heat resistance is deteriorated.

The glass transition temperature of the modified polyolefin resin is preferably 0 ° C. or less by the same measurement method as that for the polyester resin. Preferably, it is -30 degrees C or less. Those having a glass transition temperature exceeding 0 ° C. are slightly inferior in impact resistance, particularly inferior in low-temperature impact resistance. Furthermore, it is more preferable that the Young's modulus at room temperature is 250 MPa or less and the elongation at break is 200% or more, more desirably the Young's modulus is 100 MPa or less and the elongation at break is 500% or more. The molecular weight is not particularly limited, but the number average molecular weight is preferably 2 × 10 ³ or more and 1 × 10 ⁶ or less. If it is less than 2 × 10 ³ or exceeds 1 × 10 ⁶ , the mechanical performance may be inferior and impact resistance may be lowered, and molding may be difficult.

  The functional group derived from carboxylic acid is contained in an amount of 2 to 20% by weight, more preferably 3 to 12% by weight in terms of weight ratio in terms of carboxylic acid. In this composition range, the affinity with the polyester resin and the dispersibility are maximized, so that the modified polyolefin resin has a stronger affinity with the matrix polyester resin, so that the effect of mitigating the interlaminar fracture between different resins increases at the time of impact, As a result, the impact resistance becomes high, and further, the aggregation of the modified polyester particles during the molding process is suppressed. As a result, the variation in performance due to the molding conditions is reduced. Such an effect is obtained when the weight ratio of the functional group in terms of carboxylic acid is 2% by weight or more. On the other hand, when the weight ratio exceeds 20% by weight, the affinity with the polyester resin is decreased, resulting in poor impact resistance.

  In the present invention, it is specified that the amount of the modified polyolefin resin present in the mixed resin in a granular state with a particle size of 0.1 to 5 μm is in the range of 3 to 25 vol% in terms of the volume fraction in the mixed resin. As described above, particles having a particle size of less than 0.1 μm have no effect on the physical properties of the mixed resin. On the other hand, particles having a particle size of more than 5 μm do not improve the physical properties such as the processability of the mixed resin, or rather. Therefore, the granular modified polyester resin that contributes to the improvement of impact resistance has only a particle diameter of 0.1 to 5 μm in terms of equivalent spherical equivalent diameter. Since the physical properties of the film can be arranged by the absolute value of the volume of the particles of this size in the whole film, the volume fraction was specified to be in the range of 3 to 25 vol%. If the volume ratio of the modified polyolefin resin is less than 3 vol%, the impact resistance is insufficient, and if it exceeds 25 vol%, the performance such as processability is deteriorated.

Furthermore, the number of modified polyolefin resins present in the mixed resin layer in a granular state with a particle diameter of 0.1 to 5 μm in a cube having a side of 10 μm (volume of 1000 μm ³ ) in the mixed resin is 5 to 10 ^5. A range of pieces is preferred. More preferably from ⁴ 50 to 10. In less than five is insufficient in improving the impact resistance decreases the performance of workability and more than 10 ^5.

  The thickness of the resin film made of the mixed resin is preferably in the range of 10 to 50 μm. The upper limit is from an economical viewpoint, and the lower limit is from the viewpoint of impact resistance and workability. That is, when the film thickness is 10 μm or more, the impact resistance and workability are more excellent, but when the film thickness exceeds 50 μm, the cost of the resin film increases and the effect of improving the impact resistance and workability is saturated. is there.

  A method for producing the modified polyolefin resin will be described below. Functional groups derived from carboxylic acids include carboxylic acid groups, carboxylic ester groups, metal salts of carboxylic acid ions, etc., and monomers containing these functional groups are copolymerized, graft polymerized, or blocked in polyolefin resins. A carboxylic acid-modified polyolefin is obtained by polymerization.

  Specific examples of the monomer containing a functional group derived from carboxylic acid include 3 carbon atoms such as acrylic acid, methacrylic acid, vinyl acetate, vinyl propionate, maleic acid, maleic anhydride, itaconic acid, and maleic acid monomethyl ester. -8 unsaturated carboxylic acids, and metal salts in which all or part of these acids are neutralized with a divalent metal cation such as sodium, potassium, lithium, zinc, magnesium, calcium and the like. The degree of neutralization is preferably 20 to 80%, more preferably 30 to 70%, and the composition formed from the modified polyolefin resin having such a degree of neutralization is excellent in melt extrudability.

  Examples of the carboxylic acid ester include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isobutyl acrylate, isobutyl methacrylate, n-butyl acrylate, Examples include n-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, monomethyl maleate, glycidyl acrylate, glycidyl methacrylate, vinyl acetate, acrylic amine, and acrylamide.

  These carboxylic acid-derived functional group-containing monomers are copolymerized or blocked with carboxylic acid-derived functional group-free olefin monomers such as ethylene, propylene, 1-butene, 1-pentene, isobutene, isobutylene, butadiene, styrene, acrylonitrile, etc. Carboxylic acid-derived functional group-containing modified polyolefin resin can be obtained by polymerization or graft polymerization. Among these, in particular, those obtained by graft polymerization or copolymerization of a carboxylic acid group in a polyolefin resin exhibit high performance. A commercially available resin can also be used as such a modified polyolefin resin. For example, Modiper A (manufactured by Nippon Oil & Fats Co., Ltd.), Nucrel (manufactured by Mitsui DuPont Polychemical Co., Ltd.), Bondine (manufactured by Sumitomo Chemical Co., Ltd.), Admer (manufactured by Mitsui Chemicals Co., Ltd.), And Tuftec (manufactured by Asahi Kasei Corporation).

  Further, those obtained by partially neutralizing these carboxylic acids with metal salts can also be used. Although such a resin has a slightly reduced workability, a resin having a higher impact resistance can be obtained. Examples of commercially available resins include High Milan (Mitsui DuPont Polychemical Co., Ltd.). Furthermore, when zinc oxide, calcium hydroxide, or the like is added when the carboxylic acid-modified polyolefin resin is melt-dispersed in the polyester resin, the carboxyl groups in the modified polyolefin resin are neutralized with those metal ions, resulting in the carboxylic acid being A product having a structure in which a carboxylic acid-modified polyolefin resin partially neutralized with a metal salt is dispersed in a polyester resin is obtained.

  A mixed resin as a raw material is obtained by dispersing the modified polyolefin resin in the polyester resin. As a dispersion method, for example, two resins are melted and mixed, maintained at a temperature to become one phase, then cooled to a temperature at which the two phases are separated, and modified polyolefin resin in the polyester resin phase using phase separation. A method of dispersing phases, a method of evaporating a solvent after dissolving two resins in a common solvent, and a modified polyolefin resin whose primary particle size has been refined to 1 μm or less in advance is melted at a temperature that does not aggregate in the polyester resin. The polyester resin is produced by polymerizing a monomer in a solution containing a modified polyolefin resin and a polyester resin constituent monomer whose primary particle size is refined to 1 μm or less in advance, and the modified polyolefin resin is dispersed in the polyester. The method of making it into a state, and also two modified resins are melt-mixed and modified with a mechanical shear force There is a method of refining the olefin resin, and any method is possible.

  As a mixing and melting apparatus, a mixing apparatus such as a tumbler blender, a Henschel mixer, or a V-shaped blender, or a melt mixing apparatus such as a single or twin screw extruder, a kneader, or a Banbury mixer can be used. Temperature control such as temperature control and temperature change is made stricter than normal mixing method, mixing time is made 3 to 10 times longer than normal mixing time, mechanical shear rate at the time of mixing By, for example, 2 to 5 times faster than the normal speed, or by combining them, for example, mechanically mixing with a tumbler blender and then melt-mixing with an extruder. A highly dispersible mixed resin in which a granular modified polyolefin resin having a particle diameter of 0.1 to 5 μm is previously dispersed in a plastic polyester resin. It is. By forming a film of a highly dispersible mixed resin obtained by melt-mixing with an extruder, a resin film having a more uniform particle diameter of the modified polyolefin resin can be obtained, and as a result, performance such as impact resistance is enhanced. “By blending a highly dispersed resin with such a particle size into an extruder and melting it into a film, the particle size of the granular resin is far greater than dispersing the modified polyolefin resin while forming the film. As a result, a film that can exhibit excellent performance in various performances is obtained.

  On the other hand, as long as the effect of the present invention is not hindered, the light stabilizer, impact resistance improver, compatibilizer, lubricant, plasticizer, antistatic agent, reaction catalyst, anti-coloring agent, radical inhibitor in the mixed resin, Additives such as plasticizers, antioxidants, end-capping agents, heat stabilizers, mold release agents, flame retardants, antibacterial agents, and antifungal agents may be added. In the present invention, the content of these additives is preferably 0.005 to 15 parts by weight with respect to 100 parts by weight of the mixed resin. More preferably, it is 0.01 parts by weight or more and 2 parts by weight or less, and particularly preferably 0.05 parts by weight or more and 0.5 parts by weight or less. If the amount is less than 0.005 parts by weight, the effect is insufficient. On the other hand, if the amount exceeds 15 parts by weight, the additive becomes excessive and the mechanical performance of the mixed resin layer is lowered.

  Inorganic particles that are effective in improving slipperiness, moldability, impact resistance, etc. include silica produced by dry and wet methods, porous silica, colloidal silica, titanium oxide, zirconium oxide, aluminum oxide, carbonic acid Calcium, talc, calcium sulfate, barium sulfate, spinel, iron oxide, calcium phosphate and the like, and as organic particles or organic polymer particles, polystyrene particles, crosslinked polystyrene particles, styrene-acrylic crosslinked particles, acrylic crosslinked particles, Organic polymer particles composed of vinyl resin particles such as styrene-methacrylic acid resin crosslinked particles and methacrylic acid resin crosslinked particles, and silicone, benzoguanamine-formaldehyde, polytetrafluoroethylene, polyphenyl ester, phenol resin, and the like. To mention That. The particle diameter and content of these particles are not particularly limited, but in order to maximize performance, the particle diameter is preferably in the range of 0.01 to 5 μm, more preferably 0.1 to 2.5 μm. The range of is preferable. Their particle size distribution is sharp and a standard deviation of 0.5 or less is preferable. Further, the shape of the particles is preferably close to a true sphere, and the ratio of major axis / minor axis is preferably 1.0 to 1.2.

  Examples of the reaction catalyst include an alkali metal compound, an alkaline earth metal compound, a zinc compound, a lead compound, a manganese compound, a cobalt compound, and an aluminum compound, and examples of the coloring inhibitor include a phosphorus compound.

  Examples of the radical inhibitor include one or more selected from phenol-based radical inhibitors, phosphorus-based radical inhibitors, sulfide-based radical inhibitors, and nitrogen-based radical inhibitors.

  As a plasticizer, a polybasic acid component having a molar ratio of an aromatic polybasic acid having 8 to 20 carbon atoms or an ester derivative thereof to a fatty acid polybasic acid having 2 to 20 carbon atoms or an ester derivative thereof is 0 to 2.0. And an aliphatic alcohol having 2 to 20 carbon atoms subjected to terminal polymerization with a monobasic acid having 2 to 20 carbon atoms or an ester derivative thereof and / or a monohydric alcohol having 1 to 18 carbon atoms. Mention may be made of plasticizers made of polyester.

  As an antistatic agent, a resin composition such as an antistatic agent disclosed in Patent Document 12 is used for the purpose of preventing electrostatic disturbance such as winding of a film around a roll in a film forming process and adhesion of dirt on the film surface. A method of kneading into a product or a method of applying an antistatic agent described in Patent Document 13 to the film surface can be applied as necessary.

  As the antibacterial agent, conventionally known antibacterial agents disclosed in Patent Document 14, Patent Document 15 and the like can be used as necessary.

  A polyester resin polymerization catalyst is added to the mixed resin. The polymerization catalyst preferably contains 1 ppm or more and 500 ppm or less of at least one element selected from germanium, antimony, and titanium. More preferably, it is 3 ppm or more, and further preferably 10 ppm or more. If the amount of at least one element selected from germanium, antimony, and titanium is less than 1 ppm, the effect of improving the flavor may not be sufficient, and if it exceeds 500 ppm, foreign matter is generated in the polyester, which becomes a crystal nucleating agent and easily crystallizes. Therefore, the impact resistance may be deteriorated or the heat resistance may be reduced. Among these elements, germanium element is particularly preferable from the viewpoint of flavor.

  The compound used to contain at least one element selected from germanium, antimony, and titanium in the polyester resin of the present invention is, for example, germanium oxide such as germanium dioxide or crystal water-containing germanium hydroxide. , Hydroxide, or germanium alkoxide compounds such as germanium tetramethoxide, germanium tetraethoxide, germanium tetrabutoxide, germanium ethyleneglycoxide, germanium phenoxide compounds such as germanium phenolate and germanium β-naphtholate, germanium phosphate, phosphorus Examples thereof include phosphorus-containing germanium compounds such as germanium acid and germanium acetate.

  Examples of the antimony compound include antimony trioxide, antimony trifluoride, antimony acetate, antimony borate, antimony formate, and antimony acid.

  Titanium compounds include oxides such as titanium dioxide, hydroxides such as titanium hydroxide, alkoxide compounds such as tetramethoxy titanate, tetraethoxy titanate, tetrapropoxy titanate, tetraisopropoxy titanate, tetrabutoxy titanate, and tetrahydroxyethyl titanate. And the like such as a glycoxide compound, a phenoxide compound, and an acetate salt.

  The method for incorporating the above-mentioned elements into the polyester resin can be any conventionally known method and is not particularly limited, and is usually added as a polymerization catalyst at any stage before the production of the polyester is completed. It is preferable. As an example of such a method, the case of germanium is taken as an example. A method of adding a powder of a germanium compound as it is, or, as described in Patent Document 16, germanium in a glycol component which is a starting material of polyester. Examples thereof include a method in which a compound is dissolved and added.

  When the modified polyolefin resin containing a carboxylic acid specified in the present invention is mixed with a polyester resin, a polymerization catalyst usually mixed with the polyester resin and an antioxidant generally used for stabilizing the vinyl polymer When the agent coexists, the resin deteriorates and the performance decreases. The mechanism by which the resin deteriorates and the performance decreases is not necessarily clear, but it is assumed that the antioxidant acts on the polymerization catalyst, reduces the effect of the polymerization catalyst, and in particular produces a compound that degrades the polyester resin. Yes. Therefore, in the present invention, the ratio X / Y (weight ratio) between the polymerization catalyst amount X and the antioxidant amount Y added to the mixed resin needs to be 0.2 or more. Further, the antioxidant is preferably 500 ppm or less. Examples of such antioxidants include one or more selected from phenol-based antioxidants, phosphorus-based antioxidants, sulfide-based antioxidants, and nitrogen-based antioxidants.

As the mechanical performance of the resin film made of a mixed resin to cope with severe molding, it is desirable that the breaking elongation is 20% or more, preferably 50% or more, and the breaking strength is 20 N / mm ² or more. Here, the elongation at break and the strength at break of the resin film are determined by a normal tensile testing machine. As a tensile test method, a resin coating layer of 5 mm × 60 mm is set at a distance between chucks of 30 mm, and a tensile test can be performed at a constant temperature of 25 ° C. and a tensile speed of 20 mm / min. When the tensile property at low temperature is obtained, it can be obtained by conducting a similar tensile test at a constant temperature of 0 to 5 ° C. The resin sample for the test may be collected from any of a film, a resin laminated metal plate, or a molded body.

  In the present invention, it is specified that the resin film contains 5 to 40% by weight of pigment. In the polyester resin in which the modified polyolefin resin is dispersed, the dispersibility of the pigment is improved, and the desired color tone can be obtained by adding a smaller amount of the pigment. If the pigment is less than 5% by weight, the desired color tone cannot be obtained, and if it exceeds 40% by weight, the processability deteriorates. The type of pigment is not particularly limited, but unless it impedes the effects of the present invention, calcium carbonate, barium sulfate, barium carbonate, aerosil, titanium dioxide, zinc white, gloss white, alumina white, magnesium carbonate, carbon black , Magnetite, cobalt blue, bengara and the like are used as appropriate, and the metal laminate plate or metal can can be finished in a preferable color tone.

  The resin film made of the above mixed resin is superior in adhesion to the base metal compared to a normal polyester resin, and exhibits high processability and impact resistance, as well as sufficient flavor for normal use. Therefore, it can be suitably used as a resin film for metal plate lamination.

  However, the resin film made of the mixed resin may have insufficient adhesion to the base metal when subjected to more severe processing. In recent years, depending on the application, there are many people who are very sensitive to changes in flavor, and there are very strict requirements. In response to such a requirement, the resin film made of the mixed resin contains an olefin component and may have insufficient flavor properties.

  Such a problem uses a film in which a modified polyolefin resin layer containing a carboxylic acid is laminated on a resin layer made of the above-mentioned mixed resin or a polyester resin layer not containing a polyolefin resin as a resin film. It is solved by doing. The multilayer resin film will be described below.

  (1) A resin film is mainly composed of a modified polyolefin resin having a functional group derived from a carboxylic acid on a resin layer (also referred to as R1 layer or mixed resin layer in the present specification) made of the mixed resin. A film having a structure in which a resin layer (also referred to as an R2 layer in this specification) is laminated is designed so that when laminated on a metal plate, the R2 layer serves as an adhesion layer with a base metal.

  The film having the above structure can dramatically improve the adhesion after processing and heating. Furthermore, since this modified polyolefin resin layer (R2 layer) is also excellent in adhesiveness with the mixed resin layer (R1 layer), there is no delamination and the entire adhesiveness can be maintained. About this mechanism, the following is estimated. That is, the polyester resin is a resin with few functional groups that has a chemical bond with the base metal, and the metal adhesion is not high. On the other hand, a modified polyolefin resin having a carboxylic acid derivative group is characterized in that the carboxylic acid derivative group contained in the resin has a strong interaction with the base metal and has very high adhesion, but is inferior in heat resistance and flavor. Therefore, it could not be used as a film for can inner surfaces. Therefore, if such a modified polyolefin resin layer is used as an adhesion layer with a base metal and a polyester resin layer is laminated thereon, a film that achieves both adhesion and other performances such as heat resistance and flavor can be obtained. As expected, since the two resins have very different melt viscosities and melting points, the interlayer adhesion when the two resins are laminated is very inferior, and such a multilayer film cannot actually be produced. In the present invention, the modified polyolefin resin having the same composition as that of the modified polyolefin resin layer (R2 layer) which is the adhesion layer is mixed in the mixed resin layer (R1 layer), so that adhesion between the layers is a problem in terms of manufacturing and practical use. Two effects of improving the workability and impact resistance can be achieved at the same time by making the modified polyolefin resin mixed with the polyester resin into a granular form while increasing to a non-existing level.

  A film in which the mixed resin layer (R1 layer) and the modified polyolefin resin layer (R2 layer) are laminated can be obtained by an ordinary multilayer resin extrusion method. That is, using two extruders, mixed resins obtained by dispersing granular modified polyolefin resins having a particle diameter of 0.1 to 5 μm in thermoplastic polyester resin as raw material resins for the R1 layer in different extruders in advance As a raw material resin for the R2 layer, a resin mainly composed of a modified polyolefin resin having a functional group derived from a carboxylic acid is inserted, melted to a temperature higher than the melting point of the resin, and one by a feed block method or a multi-manifold method. Extruded in a state of being laminated from a T-die, cooled with a cooling roll or the like to form a multilayer film, and then laminated onto a metal plate, or directly extruded from a molten resin onto a metal plate and then sandwiched with a cooling roll for lamination Thus, a multi-layered resin layer can be manufactured by the direct laminating method. As the T-die method, it is particularly preferable to manufacture by a multi-manifold method capable of controlling the melting temperature of a plurality of resins in detail.

  As another manufacturing method, since the surface tension of the modified polyolefin resin is smaller than that of the polyester resin, the modified polyolefin resin is concentrated on the surface of the mixed resin while the molten mixed resin is cooled. Even if both resins are inserted into a single extruder, melt mixed and then extruded from the T-die, the modified polyolefin resin is concentrated on the surface of the mixed resin by slowing the cooling rate, etc. Can be manufactured.

  The thickness ratio R1 / R2 between the R1 layer and the R2 layer is such that R1 / R2 = 1/1 to 20/1 is a composition that maximizes mechanical properties such as workability and impact resistance and adhesion, R1 / R2 = 5/1 to 10/1 is preferable. If the R1 layer is thinner than this, the mechanical properties are very poor, whereas if the R2 layer is thinner than this, the adhesion is poor. Furthermore, the optimal film thickness of the modified polyolefin resin layer of the R2 layer is 1 to 10 μm, and more preferably 1 to 5 μm. If the thickness is less than 1 μm, the adhesion is insufficient. On the other hand, if the thickness is 10 μm or more, the high-impact resistance and processability of the R1 layer olefin-dispersed polyester resin are lost. Similarly, the optimum film thickness of the modified olefin-dispersed polyester resin layer of the R1 layer is 10 to 50 μm, and more preferably 15 to 25 μm. If the thickness is less than 10 μm, the development of impact resistance and workability is insufficient. On the other hand, if the thickness exceeds 50 μm, the performance is not improved and the cost is disadvantageous.

  Furthermore, the optimal composition of the modified polyolefin resin of the R2 layer is also the same as the modified polyolefin in the mixed resin of the R1 layer, and the functional group derived from carboxylic acid is preferably 2 to 20% by weight in terms of carboxylic acid, more preferably It is preferable to contain 3 to 12% by weight. In terms of adhesion after severe processing and impact, adhesion between the R1 layer mixed resin and the modified polyolefin resin of the R2 layer is important as well as adhesion between the base metal and the resin. This is because it is based on the interaction between the modified polyolefin resins, and therefore it is advantageous to have a close resin composition. Here, the weight ratio in terms of carboxylic acid means that all functional groups derived from the carboxylic acid contained in the modified polyolefin resin are converted into carboxylic acid by hydrolysis or neutralization with an acid, The amount of carboxylic acid groups (—COOH) is shown by weight ratio.

  (2) On the mixed resin layer (R1 layer), a polyester resin layer (hereinafter also referred to as R0 layer) having polyethylene terephthalate and / or isophthalic acid copolymerized polyethylene terephthalate as a main basic skeleton was laminated. A film having a structure is designed so that the R0 layer becomes the outermost layer when laminated on a metal plate.

  Polyester resin comprising polyethylene terephthalate and / or isophthalic acid copolymer polyethylene terephthalate as the main basic skeleton means a part of the polyester resin skeleton containing only ethylene glycol and terephthalic acid as a structural unit and / or ethylene glycol, terephthalic acid and isophthalic acid The total of the parts having the structural units occupy 90% by weight or more, and the acid component may optionally copolymerize various aromatic dicarboxylic acids and aliphatic dicarboxylic acids at other sites.

  Since the R1 layer is flexible, the copolymerized polyester resin may be inferior in heat resistance and flavor properties. The resin layer (R1 layer) made of the mixed resin in which the modified polyolefin resin is dispersed is the lower layer, the polyester resin not containing olefin (R0 layer) is the upper layer, and the R0 layer is a layer in contact with the contents. As a result, the flavor of the film is dramatically increased. As a result, the flavor can be increased to a level that can meet the above-mentioned strict requirements. The slight olefin portion contained in the polyester resin has a higher sorption of terpene hydrocarbons such as d-limonene, which is a fragrance component, than the polyester portion, and therefore the fragrance sorption as a whole compared to the polyester resin not containing olefin. Therefore, when the content containing the fragrance touches the film, the amount of the fragrance component transferred to the film from the content increases. In order to suppress such a phenomenon, it is effective to provide a polyester resin layer not containing an olefin component on a polyester resin containing an olefin component. In addition, mechanical properties such as workability and impact resistance can be improved.

  The optimum film thickness of the upper layer (R0 layer) is 1 to 10 μm, and more preferably 3 to 5 μm. If the thickness is less than 1 μm, the effect of suppressing the sorption of the perfume component can hardly be expected. On the other hand, if the thickness is 10 μm or more, the high-level impact resistance and processability of the lower olefin-dispersed polyester resin are lost. The optimum film thickness of the lower layer (R1 layer) is 10 to 50 μm, more preferably 15 to 25 μm. If the thickness is less than 10 μm, the development of impact resistance and workability is insufficient. On the other hand, if the thickness exceeds 50 μm, the performance is not improved and the cost is disadvantageous.

  The total film thickness of the film including the R1 layer and the R0 layer is more preferably in the range of 10 to 50 μm. The upper limit is from an economical viewpoint, and the lower limit is from the viewpoint of impact resistance and workability. That is, when the film thickness is 10 μm or more, the impact resistance and workability are more excellent, but when the total film thickness exceeds 50 μm, the cost of the resin film increases and the effect of improving the impact resistance and workability is saturated. It is.

  Furthermore, the mechanical properties such as workability and impact resistance and flavor properties are such that the thickness ratio R1 / R0 of the lower layer (R1 layer) and the upper layer (R0 layer) is R1 / R0 = 2/1 to 10/1. 5/1 to 10/1 is more preferable. If the R0 layer is thicker than this, the mechanical properties are very inferior. On the other hand, if the R0 layer is thinner than this, the R0 layer and the R1 layer will not have a uniform film thickness ratio in the line direction and width direction during manufacturing, resulting in variations in performance. Inferior performance.

  The polyester resin of the R0 layer preferably has a diethylene glycol content of 1.5% by weight or less, more preferably 0.9% by weight or less. When the polyester contains a large amount of diethylene glycol, the deterioration of the polymer progresses due to heat treatment such as drying during printing and printing, and cracks and pinholes occur, resulting in poor impact resistance and flavor. There is.

  The intrinsic viscosity of the polyester resin of the R0 layer is 0.3 to 2.0 dl / g, more preferably 0.3 to 1.5 dl / g, and still more preferably 0.5 to 1.0 dl / g. If it is less than 0.3 dl / g, mixing with the modified polyolefin resin becomes extremely difficult, and as a result of the modified polyolefin resin not being uniformly dispersed, the mechanical strength and impact resistance of the polyester resin may be reduced, When the intrinsic viscosity exceeds 2.0 dl / g, since the viscosity is low, the moldability becomes poor and it may be difficult to produce a uniform film. The intrinsic viscosity is measured by the method shown in JIS K7367-5, and is measured at a concentration of 0.005 g / ml in o-chlorophenol at 25 ° C. The intrinsic viscosity = (T−T0) / It is obtained by the equation (T0 * c). In the formula, c represents the concentration of the resin per 100 ml of the solution expressed in grams, and T0 and T represent the flow time of the solvent and the resin solution in the capillary viscometer, respectively.

  The polyester resin of the R0 layer preferably has a glass transition temperature (Tg) of 30 to 100 ° C, more preferably 50 to 80 ° C. When the glass transition temperature is less than 30 ° C, the heat resistance of the polyester resin is inferior, so that scratches and the like are likely to occur due to the temperature rise during molding. Inferior. The low temperature crystallization temperature (Tc) is usually 70 to 210 ° C., preferably 80 to 200 ° C., and the melting point (Tm) is usually 210 to 265 ° C., preferably 220 to 260 ° C. . If the low-temperature crystallization temperature is less than 70 ° C, crystallization is likely to occur, so that crystallization occurs during retort treatment, etc., and the film is likely to crack or peel off, while those exceeding 210 ° C are inferior in mechanical strength of polyester. . If the melting point is less than 210 ° C, the resin deteriorates due to heat during molding, and cracks and pinholes are likely to occur. On the other hand, those that exceed 265 ° C are crystallized by heat treatment such as drying and printing baking during molding. As a result, cracks and pinholes are likely to occur. The glass transition temperature, the low-temperature crystallization temperature, and the crystal melting temperature are obtained by measuring the endothermic peak temperature at the time of temperature rise using a differential scanning calorimeter (DSC). It is a value measured under the condition of minutes.

  A film obtained by laminating a mixed resin layer (R1 layer) and a polyester resin layer (R0 layer) having polyethylene terephthalate and / or isophthalic acid copolymerized polyethylene terephthalate as a main basic skeleton is obtained by an ordinary multilayer resin extrusion method. be able to. That is, using two extruders, different extruders, as a raw material resin for the R1 layer, granules having a particle diameter of 0.1 to 5 μm in the thermoplastic polyester resin according to claim 1. A mixed resin in which the modified polyolefin resin is dispersed in advance and a polyester resin mainly composed of polyethylene terephthalate and / or isophthalic acid copolymerized polyethylene terephthalate as the raw material resin for the R0 layer are inserted and melted above their melting points. Then, it is extruded in a state where it is laminated from one T die by the feed block method or the multi-manifold method, and cooled with a cooling roll or the like to form a multilayer film and then laminated on the metal plate or directly on the metal plate Direct laminating by laminating by laminating with a cooling roll after extruding molten resin Resin layer of a double layer can be produced by over preparative method. As the T-die method, it is particularly preferable to manufacture by a multi-manifold method capable of controlling the melting temperature of a plurality of resins in detail.

  In addition, as long as the effects of the present invention are not hindered, the light stabilizer, impact resistance improver, compatibilizer, lubricant, plasticizer, antistatic agent, reaction catalyst, anti-coloring agent, radical inhibitor, R0 layer polyester resin, You may add additives, such as a plasticizer, an antistatic agent, a terminal blocker, antioxidant, a heat stabilizer, a mold release agent, a flame retardant, an antibacterial agent, and an antifungal agent. The content of these additives is preferably 0.005 parts by weight or more and 15 parts by weight or less in the present invention with respect to 100 parts by weight of the polyester resin of the R0 layer. More preferably, it is 0.01 parts by weight or more and 2 parts by weight or less, and particularly preferably 0.05 parts by weight or more and 0.5 parts by weight or less. If the amount is less than 0.005 parts by weight, the effect is insufficient. On the other hand, if the amount exceeds 15 parts by weight, the additive becomes excessive, and the components contained in the polyester resin phase deteriorate the mechanical performance.

  Inorganic particles effective in improving slipperiness, molding processability and impact resistance include dry and wet silica, porous silica, colloidal silica, titanium oxide, zirconium oxide, aluminum oxide, calcium carbonate, talc, sulfuric acid Calcium, barium sulfate, spinel, iron oxide, calcium phosphate, etc., and organic particles or organic polymer particles include polystyrene particles, crosslinked polystyrene particles, styrene-acrylic crosslinked particles, acrylic crosslinked particles, styrene-methacrylic crosslinked particles, methacrylic Examples thereof include particles containing vinyl-based particles such as system-crosslinked particles, silicone, benzoguanamine-formaldehyde, polytetrafluoroethylene, polyphenyl ester, phenol resin and the like. The particle diameter and content of these particles are not particularly limited, but in order to maximize performance, the particle diameter is preferably in the range of 0.01 to 5 μm, more preferably 0.1 to 2.5 μm. The range of is preferable. Their particle size distribution is sharp and a standard deviation of 0.5 or less is preferable. Further, the shape of the particles is preferably close to a true sphere, and the ratio of major axis / minor axis is preferably 1.0 to 1.2.

  Examples of the reaction catalyst include an alkali metal compound, an alkaline earth metal compound, a zinc compound, a lead compound, a manganese compound, a cobalt compound, and an aluminum compound. Examples of the coloring inhibitor include a phosphorus compound.

  Examples of the radical inhibitor include one or more selected from phenol-based radical inhibitors, phosphorus-based radical inhibitors, sulfide-based radical inhibitors, and nitrogen-based radical inhibitors.

  As a plasticizer, the polybasic acid component whose molar ratio of the C8-20 aromatic polybasic acid or its ester derivative to the C2-20 fatty acid polybasic acid or its ester derivative is 0 to 2.0. A polyester obtained by polycondensation of an aliphatic alcohol having 2 to 20 carbon atoms with a monobasic acid having 2 to 20 carbon atoms or an ester derivative thereof and / or a monohydric alcohol having 1 to 18 carbon atoms. The plasticizer which consists of can be mentioned.

  As an antistatic agent, a resin composition such as an antistatic agent disclosed in Patent Document 12 is used for the purpose of preventing electrostatic disturbance such as winding of a film around a roll in a film forming process and adhesion of dirt on the film surface. A method of kneading into a product or a method of applying an antistatic agent described in Patent Document 13 to the film surface can be applied as necessary.

  As the antibacterial agent, conventionally known antibacterial agents disclosed in Patent Document 14, Patent Document 15 and the like can be used as necessary.

  The polyester resin of the R0 layer preferably contains 1 to 500 ppm of at least one element selected from germanium, antimony, and titanium as a polymerization catalyst. More preferably, it is 3 to 300 ppm. If the amount of at least one element selected from germanium, antimony, and titanium is less than 1 ppm, the effect of improving the flavor may not be sufficient, and if it exceeds 500 ppm, foreign matter is generated in the polyester, which becomes a crystal nucleating agent and easily crystallizes. Therefore, the impact resistance may be deteriorated or the heat resistance may be reduced. Among these elements, germanium element is particularly preferable from the viewpoint of flavor.

  The compound used to contain at least one element selected from germanium, antimony, and titanium in the resin of the present invention is, for example, germanium oxide, germanium oxide such as germanium hydroxide containing crystal water, Hydroxides or germanium alkoxide compounds such as germanium tetramethoxide, germanium tetraethoxide, germanium tetrabutoxide, germanium ethyleneglycoxide, germanium phenoxide compounds such as germanium phenolate and germanium β-naphtholate, germanium phosphate, phosphorous acid Examples include phosphorus-containing germanium compounds such as germanium, germanium acetate, and the like.

  Examples of the antimony compound include antimony trioxide, antimony trifluoride, antimony acetate, antimony borate, antimony formate, and antimony acid.

  Titanium compounds include oxides such as titanium dioxide, hydroxides such as titanium hydroxide, alkoxide compounds such as tetramethoxy titanate, tetraethoxy titanate, tetrapropoxy titanate, tetraisopropoxy titanate, tetrabutoxy titanate, and tetrahydroxyethyl titanate. And the like such as a glycoxide compound, a phenoxide compound, and an acetate salt.

  The method of incorporating the above-mentioned elements into the polyester can be any conventionally known method, and is not particularly limited. Usually, it is added as a reaction catalyst at any stage before the production of the polyester is completed. Is preferred. As an example of such a method, the case of germanium is taken as an example. A method of adding a powder of a germanium compound as it is, or, as described in Patent Document 16, germanium in a glycol component which is a starting material of polyester. Examples thereof include a method in which a compound is dissolved and added.

  The polyester resin of the R0 layer of the present invention preferably has an acetaldehyde content in the resin of 10 ppm or less, more preferably 7 ppm or less, from the viewpoint of flavor. If the acetaldehyde content exceeds this range, particularly 10 ppm, the flavor properties may be inferior. The method for setting the acetaldehyde content to 10 ppm or less is not particularly limited. For example, in order to remove acetaldehyde generated by thermal decomposition when a polyester resin is produced by polycondensation reaction or the like, the resin was obtained by a method of heat-treating the resin at a temperature below the melting point of the polyester under reduced pressure or in an inert gas atmosphere. Examples include a method of forming a polyester resin into a film, and a method using a polyester resin obtained by solid-phase polymerization at a temperature of 150 ° C. or higher and a melting point or lower in a reduced pressure or inert gas atmosphere is preferable.

  Further, the polyester resin of the present invention preferably has fewer oligomers composed of a cyclic trimer or the like in the resin from the viewpoint of flavor. In particular, the content of the cyclic trimer is preferably 0.9% by weight or less, and particularly preferably 0.7% by weight or less. If the oligomer content in the resin exceeds this range, particularly 0.9% by weight, the flavor properties may be inferior. The method for setting the oligomer content to 0.9% by weight or less is not particularly limited, but can be achieved by adopting a method similar to the method for reducing the acetaldehyde content described above.

  When an antioxidant is added to the R0 layer, it is preferable to add the same amount as that of the R1 layer in order to minimize the influence on the R1 layer.

  (3) A polyester resin layer (R0 layer) mainly composed of polyethylene terephthalate copolymerized with polyethylene terephthalate and / or isophthalic acid is laminated on one surface of a resin layer (R1 layer) made of a mixed resin, The R0 layer / R1 layer / R2 layer 3 in which a resin layer (R2 layer) mainly composed of a modified polyolefin resin having a functional group derived from a carboxylic acid is laminated on the other surface of the R1 layer. The film has a layer structure and is designed so that the R0 layer becomes the outermost layer when laminated on a metal plate.

  This film is obtained by laminating the R0 layer described in the above (1) on the R1 layer of the resin film having a two-layer structure composed of the R1 layer / R2 layer described in (2). This film having a three-layer structure is excellent in adhesion to the base metal and excellent in flavor. The configurations and operational effects of the R1 layer, R0 layer, and R2 layer are the same as those described in the above (1) and (2). Further, in such a three-layer structure, the adhesion is enhanced, and the stress relaxation effect is enhanced, so that defects are hardly caused in the processing, and the workability is dramatically increased.

  The film having the three-layer structure of R0 layer / R1 layer / R2 layer can be obtained by an ordinary multilayer resin extrusion method. That is, using three extruders, a granular modified polyolefin resin having a particle diameter of 0.1 to 5 μm is dispersed in advance in the thermoplastic polyester resin according to any one of claims 1 to 8 as a raw material for the R1 layer. At the same time, a polyester resin mainly composed of polyethylene terephthalate copolymerized with polyethylene terephthalate and / or isophthalic acid is used as the raw material resin for the R0 layer. As a raw material resin, a resin containing a modified polyolefin resin having a functional group derived from carboxylic acid as a main component is inserted into an extruder different from the above-mentioned extruder, and melted to a melting point or higher than the respective melting points. Extruded in a state of being laminated from one T die by the multi-manifold method and cooled After cooling with a roll or the like to form a multilayer film, it is laminated on a metal plate, or the resin layer of a multilayer is formed by a direct lamination method in which a molten resin is directly extruded onto a metal plate and then sandwiched between cooling rolls and laminated. It can be manufactured. As the T-die method, it is particularly preferable to manufacture by a multi-manifold method capable of controlling the melting temperature of a plurality of resins in detail.

  Furthermore, in any case, another polyester resin layer on the mixed resin layer (R1 layer) or the polyester resin layer (R0 layer) mainly composed of polyethylene terephthalate copolymerized with polyethylene terephthalate and / or isophthalic acid. It is also possible to have a layer structure in which layers are stacked. In that case, the polyester resin as the raw material of the third layer is inserted into another extruder, melted, poured into a T-die simultaneously with the other resin, and extruded from one port. When there is a resin layer (R2 layer) whose main component is a modified polyolefin resin having a functional group derived from carboxylic acid, the R2 layer needs to be designed to be on the base metal side.

  In the resin film described in the above (1) to (3), it is specified that the resin film contains 5 to 40% by weight of a pigment. In the polyester resin in which the modified polyolefin resin is dispersed, the dispersibility of the pigment is improved, and the desired color tone can be obtained by adding a smaller amount of the pigment. Therefore, the pigment is preferably added to the R1 layer. If the addition amount of the pigment in the resin film is less than 5% by weight, the desired color tone cannot be obtained, and if it exceeds 40% by weight, the processability is lowered. The type of pigment is not particularly limited, but unless it impedes the effects of the present invention, calcium carbonate, barium sulfate, barium carbonate, aerosil, titanium dioxide, zinc white, gloss white, alumina white, magnesium carbonate, carbon black , Magnetite, cobalt blue, bengara and the like are used as appropriate, and the metal laminate plate or metal can can be finished in a preferable color tone.

In the present invention, the metal plate is not particularly limited, but a metal plate made of iron and aluminum is preferable in terms of formability. In the case of a metal plate made of iron, in order to improve the resin adhesion and corrosion resistance on the surface, an inorganic oxide film layer such as chromic acid treatment, phosphoric acid treatment, chromic acid / phosphoric acid treatment, electrolytic chromic acid treatment, You may provide the chemical conversion treatment coating layer represented by the chromate process, the chromium chromate process, etc. Further, a spreadable metal plating layer, for example, a plating layer of nickel, tin, zinc, aluminum, gun metal, brass or the like may be provided. In the case of tin plating, 0.5 to 15 g / ^{m 2,} having a plating weight of the case of nickel or aluminum 1.8~20g / ^{m 2} is particularly preferable from the viewpoint of processability and resin adhesion. Such a metal plate has a thickness of usually 0.01 to 5 mm, preferably 0.1 to 2 mm. And the resin laminate layer which coat | covered the resin composition layer in the said invention on the metal plate single side | surface or both surfaces is formed.

In the case of a metal plate made of iron, the electrolytic chromate-treated steel sheet defined in the eighth invention is particularly preferable from the viewpoints of adhesion to the resin film of the present invention, corrosion resistance, and production cost. Since the resin of the present invention is excellent in adhesion after processing and heating, the optimum range of metal chromium and chromium oxide is wider than that of current resins. However, it has been found that the scope of the present invention is optimal when higher performance is desired. The The lower limit of the metal chromium amount of metallic chromium layer was defined as 50 mg / ^{m 2,} the corrosion resistance is less than 50 mg / ^{m 2,} may post-process adhesion is insufficient, defining the upper limit to 200 mg / ^{m 2} This is because if it exceeds 200 mg / m ² , the effect of improving the corrosion resistance and post-processing adhesion is saturated, and conversely the production cost increases. The The lower limit of the chromium content of metallic chromium in terms of chromium oxide was defined as 3 mg / m ^2, there is a case where adhesion is poor and less than 3 mg / m ^2, defines the upper limit to 30 mg / m ² If it exceeds 30 mg / m ² , the color tone deteriorates and the adhesion is also inferior.

  In the present invention, the reason why the plane orientation coefficient in the direction parallel to the film surface of the resin film is defined as less than 0.010 is that this range is particularly excellent in workability. The degree of processing becomes inferior as the plane orientation coefficient increases. This is because the oriented crystal prevents plastic deformation as described above, but it is at a level that does not substantially affect the workability within the range of the plane orientation coefficient of the present invention. Further, even in the area of the plane orientation coefficient of the 24th invention, it has sufficiently superior impact resistance as compared with the prior art, but the plane orientation coefficient is intentionally set in consideration of the required workability and impact resistance. It is also possible to obtain a higher impact resistance by increasing it to 0.010 or more. The orientation of the film as described above can be obtained by laminating the stretched film on a metal plate. That is, it can be obtained by heat laminating a film which has been stretched in a uniaxial or biaxial direction by a known method and imparted with a stretch orientation at the time of film production so that the orientation remains at the time of lamination. As for stretching of the film, biaxial stretching is particularly superior from the viewpoint of mechanical performance.

  As a method for producing a laminated metal plate, a known method can be used. In particular, a resin film is rotated on a metal plate heated in the range of the melting point of the polyester resin in the mixed resin of the R1 layer to −70 ° C. to the melting point + 30 ° C. A method of laminating by pressing using a roll is preferred. If the melting point of the polyester resin is less than −70 ° C., the adhesion to the metal plate is not sufficient, and if it exceeds the melting point of the polyester resin + 30 ° C., the film layer is fused to the laminate roll. Since the resin of the present invention is excellent in adhesion after processing and heating, the optimum range of production conditions in the film laminate is wider than in the case of the current resin, and labor saving and stabilization in terms of production management and quality control are achieved. It is possible and advantageous.

  As the film to be laminated, a stretch-oriented film and an unstretched film can be used. In particular, when a stretched film is used, as described above, it is necessary to control the degree of orientation to a target value by controlling the temperature during thermal lamination.

  In the case of producing a laminated metal plate, a direct laminating method in which a molten resin is extruded directly onto a metal plate and then sandwiched between cooling rolls as described below is preferable.

  When laminating a resin film made of a mixed resin on a metal plate, the thermoplastic polyester resin according to any one of claims 1 to 8 is used as a raw material resin, and has a particle size of 0.1 to 5 µm. A mixed resin in which a modified polyolefin resin is dispersed in advance is inserted into an extruder, and the resin as the raw material is heated and melted in the range of the melting point of the polyester resin in the resin to + 10 ° C. to the melting point + 50 ° C. Is directly extruded from a T-die and laminated on the surface.

  When laminating a resin film obtained by laminating the R1 layer and the R0 layer on a metal plate, the particle diameter of the thermoplastic polyester resin described in any one of claims 1 to 8 is used as a raw material for the R1 layer. Is inserted into an extruder, and at the same time, polyethylene terephthalate copolymerized with polyethylene terephthalate and / or isophthalic acid is used as a raw material for the R0 layer. A resin composed of a polyester resin having a main basic skeleton is inserted into another extruder, and heated and melted within the range of the melting point of the polyester resin of the R1 layer + 10 ° C. to the melting point + 50 ° C. Directly two-layer extrusion with the R1 layer facing the metal plate with the R1 and R0 layers laminated from the T die on the surface The laminate-.

  When laminating a resin film in which the R1 layer and the R2 layer are laminated on a metal plate, the particle diameter is 0.1 in the thermoplastic polyester resin according to any one of claims 1 to 8 as a raw material resin for the R1 layer. A resin in which a modified resin having a functional group derived from a carboxylic acid as a main component is used as a raw material resin for the R2 layer at the same time as a mixed resin in which granular modified polyolefin resin having a particle size of ˜5 μm is dispersed in advance is inserted into an extruder. After inserting them into another extruder and heating and melting them in the range of the melting point of polyester resin of the R1 layer + 10 ° C. to the melting point + 50 ° C., from the T die to the R1 layer and the R2 layer on the surface of the metal plate The two layers are directly extruded and laminated so that the R2 layer is on the metal plate side.

  When laminating a resin film having a three-layer structure of R0 layer / R1 layer / R2 layer on a metal plate, the thermoplastic resin described in any one of claims 1 to 8 is used as a raw material resin for the R1 layer. A mixed resin in which a granular modified polyolefin resin having a particle size of 0.1 to 5 μm is dispersed in advance is inserted into an extruder and melted. At the same time, polyethylene terephthalate and / or isophthalic acid is copolymerized as a raw material resin for the R0 layer. A resin composed of a polyester resin mainly composed of polyethylene terephthalate, and a resin mainly composed of a modified polyolefin resin having a functional group derived from a carboxylic acid as a raw material resin for the R2 layer; Are inserted into another extruder, and they are melted from the melting point of the polyester resin of the R1 layer + 10 ° C. to the melting point. After heating to + 50 ° C. and melting, the R0 layer, R1 layer, and R2 layer are laminated on the surface of the metal plate from the T die, the R2 layer is the metal plate side, and the R1 layer is the intermediate layer Then, the three layers are directly extruded and laminated so that the R0 layer becomes the outermost layer.

  If the melting temperature of the resin is less than the melting point of the polyester resin + 10 ° C., the viscosity of the resin is remarkably inferior, resulting in poor quality stability and productivity. If the melting point of the polyester resin exceeds the melting point + 50 ° C., the adhesion to the laminate roll This is because air bubbles are mixed in and deterioration of the resin becomes a problem. The melting point of the polyester resin + 40 ° C. or lower is more preferable. Moreover, it is preferable that the temperature of a metal plate is the range of melting | fusing point -70 degreeC-melting | fusing point +30 degreeC of the polyester resin in the mixed resin of R1 layer.

  Since the resin of the present invention does not require strict management even under the production conditions in extrusion lamination, it is advantageous in that labor saving and stabilization can be achieved in terms of production management and quality control. In addition, by mixing a resin with such a uniform particle size and high dispersibility into an extruder and melting it into a film, it is much more granular than granular resin than dispersing modified polyolefin resin while forming a film. The diameter distribution is narrowed, and as a result, a film that can exhibit excellent performance in various performances can be obtained.

  In the present invention, the reason why the resin film is limited to those coated by the extrusion laminating method is that the extrusion laminating method is superior to the ordinary film laminating method from the viewpoint of preventing bubble entrainment during lamination. In a general film laminating method, bubbles are more easily involved especially as the laminating speed increases. The entrained bubbles not only cause a decrease in adhesion with the base metal plate, but also adversely affect the impact resistance. The present inventors have found out that stress concentration occurs at the edge of a bubble in response to an impact, and that this portion is brittle and serves as a starting point for film destruction. Further, the difference in production cost caused by the difference between the step of laminating and laminating the resin and the step of directly extruding and laminating the resin is another advantage of the extrusion laminating method.

  The resin of the present invention can be produced by an extrusion laminating method, which was impossible with a conventional polyester resin, because sufficient performance can be obtained even when the resin of the present invention is substantially non-oriented. Compared to the fact that the resin requires strict control of the amount of orientation and cannot be manufactured by direct extrusion, where such control is not possible, there are significant advantages in terms of manufacturing.

  The resin-laminated metal plate of the present invention is only required to be coated with the resin film of the present invention. If necessary, a known resin film is laminated on the lower layer and / or the upper layer of the resin film of the present invention to cover the metal plate. You may do it.

  In the present invention, a primer layer may be provided as an adhesion layer with the metal plate as long as the effects of the present invention are not hindered. The laminated metal plate of the present invention is excellent in both the primary adhesion and post-processing adhesion of the resin layer and the metal plate, but in a more severe corrosive environment or an environment where better adhesion is required, the primer Layers can be provided to provide the required properties. For example, when used as a metal can, filling a more corrosive content causes the content to enter the interface with the metal plate through the resin layer, corrodes the metal plate, and deteriorates the adhesion to the film. there is a possibility. In such a case, it is possible to prevent the resin layer from peeling off by providing an appropriate primer layer. When there is no R2 layer, it is effective to provide a primer layer as an adhesion layer.

  Although the kind of primer is not specifically limited, a well-known primer layer can also be used. Examples thereof include a polyester resin-based aqueous dispersant disclosed in Patent Document 17, an epoxy primer disclosed in Patent Document 18, and a polymer having various functional groups disclosed in Patent Document 19. The method for forming the primer layer is not particularly limited, but the primer coating may be applied to the metal plate and dried, or the primer coating may be applied to the film of the present invention and dried, or the primer may be applied to the metal plate. A film may be laminated, and further, a film obtained by bonding the film of the present invention and a primer layer may be laminated.

  The resin film for laminating a metal plate of the present invention can be suitably used for inner surface coating of a two-piece metal can manufactured by drawing or ironing. In addition, the film of the present invention has good metal adhesion and moldability for covering the lid part of a two-piece can or the trunk, lid and bottom of a three-piece can, and therefore it can be preferably used for this purpose. it can. In addition, since the laminated metal plate coated with the film is excellent in workability, impact resistance, and adhesion, the thickness of the material has been reduced, and as a material used for thin-walled deep-drawn cans that are forced to be severely formed. Is preferred.

  Moreover, since the laminated metal plate coated with the film can prevent the cloudiness of the film during retort processing, the can member used for the can lid and the bottom of the can which has a strong demand for preventing the cloudiness of the film, for example, a lid member of a two-piece can Alternatively, it can be suitably used for a lid member and a can body member of a three-piece can.

<Example 1>
Using a carboxylic acid-derived group-modified polyolefin resin having a primary particle size of 0.3 μm as a starting material, a polyester resin and a tumbler blender were used at a blending ratio shown in Table 1 and Table 2 and then cold blended. Was used to obtain polyester resin raw material pellets in which the modified polyolefin resin was dispersed. The raw resin pellets were extruded from a T-die with a single screw extruder to produce a resin film having a thickness of 5 to 55 μm.

The polyester resin and carboxylic acid-derived group-modified polyolefin resin used are as follows.
1. Polyester resin (1) PET / I (18): ethylene phthalate-ethylene isophthalate copolymer resin (Kanebo Gosei Co., Ltd.) having a terephthalic acid to isophthalic acid ratio of 82:18, intrinsic viscosity of 0.6 dl / g, Tg58 ° C, Tc210 ° C, Tm215 ° C, Ge content 10ppm
(2) PET / I (10): ethylene phthalate-ethylene isophthalate copolymer resin (IP121B manufactured by Kanebo Gosei Co., Ltd.) having a ratio of terephthalic acid to isophthalic acid of 90:10, intrinsic viscosity 0.6 dl / g, Tg 70 ℃, Tc170 ℃, Tm230 ℃, Ge content 10ppm
(3) PET / I (5): ethylene phthalate-ethylene isophthalate copolymer resin (manufactured by Kanebo Gosei Co., Ltd.) having a ratio of terephthalic acid to isophthalic acid of 95: 5, intrinsic viscosity 0.62 dl / g, Tg 72 ° C. , Tc156 ° C, Tm255 ° C, Ge content 20ppm
(4) PET / I (2): ethylene phthalate-ethylene isophthalate copolymer resin (Kanebo Gosei Co., Ltd.) having a ratio of terephthalic acid to isophthalic acid of 98: 2, intrinsic viscosity 0.6 dl / g, Tg 68 ° C. , Tc 150 ° C., Tm 250 ° C., Ge content 10 ppm
(5) PET: Homopolyethylene phthalate resin (EFG10 manufactured by Kanebo Gosei Co., Ltd.), intrinsic viscosity 0.62 dl / g, Tg 72 ° C., Tc 150 ° C., Tm 255 ° C., Ge content 20 ppm

2. Carboxylic acid-derived group-modified polyolefin resin (1) EM1: Polymethyl methacrylate- (ethylene-ethyl acrylate copolymer) graft copolymer (Nippon Yushi Co., Ltd. Modiper A5200), weight of carboxylic acid-derived functional group Ratio 21% by weight, glass transition temperature: −30 ° C. or lower (2) EM2: polymethyl methacrylate- (ethylene-ethyl acrylate-maleic anhydride copolymer) graft copolymer (Nippon Oil & Fats Co., Ltd. Modiper A8200), 18% by weight of carboxylic acid-derived functional group, glass transition temperature: −30 ° C. or less (3) EM3: ethylene-ethyl acrylate-maleic anhydride copolymer (bondin made by Sumitomo Chemical Co., Ltd.) HX8290), weight ratio of carboxylic acid-derived functional group 11% by weight, glass transition temperature: −30 ° C. or lower (4) EM4: ethylene Crylic acid copolymer (Nucleel N1560 manufactured by Mitsui DuPont Polychemical Co., Ltd.), weight ratio of carboxylic acid-derived functional group: 8% by weight, glass transition temperature: −30 ° C. or less (5) EM5: ethylene-methacrylic acid copolymer 50% Zn neutralized product of coalescence (Nucleal N1560 manufactured by Mitsui DuPont Polychemical Co., Ltd. partially neutralized with Zn), weight ratio of carboxylic acid-derived functional group 7% by weight, glass transition temperature: −30 ° C. The following (6) EM6: 70% Zn neutralized product of ethylene-methacrylic acid copolymer (Neutral N1035 made by Mitsui DuPont Polychemical Co., Ltd. partially neutralized with Na), weight of carboxylic acid-derived functional group 5% by weight, glass transition temperature: −30 ° C. or lower (7) EM7: ethylene-methacrylic acid copolymer (Nucrel N0200H manufactured by Mitsui DuPont Polychemical Co., Ltd.) Weight ratio of carboxylic acid-derived functional group: 1% by weight, glass transition temperature: -30 ° C. or lower (8) EM8: polystyrene- (ethylene-ethyl acrylate copolymer) graft copolymer (Nippon Yushi Co., Ltd. Modiper A5100), weight ratio of carboxylic acid-derived functional group 6% by weight, glass transition temperature: 20 ° C.
(9) EPR: ethylene-propylene rubber (EP07P manufactured by JSR Corporation), weight ratio of carboxylic acid-derived functional group 0% by weight, glass transition temperature: −30 ° C. or lower

  The pelletized carboxylic acid-derived group-modified polyolefin resin was used as a starting material and melt-kneaded at 260 ° C. with a polyester resin at the compounding ratio shown in Comparative Example 14 in Table 2 using a single-screw extruder. The resin mixed resin was extruded from a T-die to produce a resin film having a thickness of 25 μm.

  The particle diameter of the modified polyolefin resin dispersed in the resin film is determined by etching the surface polyester resin with an alkaline aqueous solution to leave the modified polyolefin particles, and measuring the major and minor diameters one by one. Sphere conversion) was calculated, and the volume ratio and the number of particles in the film per side of 10 μm were determined. The various temperatures in the table were measured by the method using DSC described above.

As the metal plate, the thickness 0.18mm for the thin deep drawn can, a thickness of 0.23mm for the DI cans, both temper degree DR9, metallic chromium layer 80 mg / ^{m 2,} chrome oxide layer 15 mg / m ² After thermocompression bonding the resin film obtained as described above to both surfaces of each metal plate heated by induction heating method using tin free steel (hereinafter referred to as TFS) of ² (metal chromium equivalent) Then, a laminated metal plate was obtained by a thermal bonding method in which water was quenched. Tables 3 and 4 show the metal plate temperature (laminating temperature) during lamination.

Regarding the plane orientation coefficient of the laminated metal plate, the refractive index was measured using an Abbe refractometer, the light source was sodium / D line, the intermediate solution was methylene iodide, and the temperature was 25 ° C. The refractive index Nx in the direction, the refractive index Ny in the width direction of the metal plate on the film surface, and the refractive index Nz in the thickness direction of the film were determined, and the plane orientation coefficient Ns was calculated from the following equation.
Planar orientation coefficient (Ns) = (Nx + Ny) / 2−Nz
In addition, the laminated metal plate obtained above can be processed, subjected to heat treatment to remove strain to produce a test can, the can processed film of the can body, impact resistance, adhesiveness after processing, The adhesion after heating was investigated.

Details of the survey method are described below.
1. Evaluation by Thinning Deep Drawing Molding A thinned deep drawing can was manufactured as follows for a laminated metal plate using TFS having a thickness of 0.18 mm, and the suitability of the thinning deep drawing can was investigated.
1-1. Can making process A laminated metal plate was subjected to first-stage drawing and redrawing under the following conditions to obtain a thin-walled deep-drawn can.
・ First stage aperture Blank diameter ... 150-160mm
1st aperture stop: aperture ratio 1.65
-Re-drawing First re-drawing: Aperture ratio: 1.25
Second re-drawing: Aperture ratio: 1.25
Curvature radius of die corner in redrawing process: 0.4mm
Wrinkle holding weight during redrawing ... 39227N (4000kg)
-Average thinning ratio of can body 40-55% of the thickness of the laminated metal plate before molding
1-2. Distortion heat treatment The processing strain of the film introduced in the can manufacturing process was heated and held for 30 seconds in a thermal environment at a film melting point of -15 ° C and then rapidly cooled.

1-3. Appropriate evaluation of thin-walled deep-drawn cans (1) Processability The following evaluation was performed according to the limit that can be made without damaging the film. In addition, a pass is a thing of evaluation more than (circle).
Limiting degree of processing (thinning ratio): Molding with an evaluation thinning ratio of 40% is impossible: XX (poor)
Molding up to 40% thinning rate: × ↑
Moldable up to 45% thinning rate: △
Molding up to 50% thinning rate: ○ ↓
Molding up to 55% thinning rate: ◎ (excellent)
(2) Evaluation of room temperature and low temperature impact resistance After applying neck processing to a can body (thinning ratio 50%) subjected to heat treatment for removing strain, filling the can body with distilled water, attaching a lid and tightening, A 0.5 kg iron ball was dropped from a height of 30 cm onto the bottom of the can to give an impact. Next, the lid is opened, and 1% saline solution is filled in the can so that the impacted part is immersed. After immersion for 5 minutes, a 6 V load is applied to the platinum electrode and the can metal part immersed in the solution. The current value after 5 minutes was read and evaluated as follows. The same test was performed at room temperature 20 ° C. and 0 ° C., with the former being room temperature impact resistance and the latter being low temperature impact resistance. In addition, a pass is a thing of evaluation more than (circle).
(Room temperature impact resistance evaluation)
Test result: Evaluation Current value is 30 mA or more: XX (poor)
Current value is 10 mA or more and less than 30 mA: × ↑
Current value is 5 mA or more and less than 10 mA: Δ
Current value is 1 mA to less than 5 mA: ○ ↓
Current value is less than 1 mA: ◎ (excellent)
(Low temperature impact resistance evaluation)
Test result: Evaluation Current value is 30 mA or more: Δ (poor)
Current value is 10 mA to less than 30 mA: ○ ↑
Current value is 5 mA or more and less than 10 mA: ◎
Current value is 1 mA to less than 5 mA: ◎◎ ↓
Current value is less than 1 mA: ◎ ◎ ◎ (excellent)
(3) Adhesiveness after processing The inner surface of the can body subjected to the heat treatment for strain removal was washed and immersed in an aqueous solution of 1.5% by weight of citric acid-1.5% by weight of sodium chloride for 24 hours. The length of the peeled resin was observed and evaluated as follows. In addition, a pass is a thing of evaluation more than (circle).
Test result: peeling exceeding evaluation 10 mm: xx (poor)
Peel off over 5mm to 10mm: × ↑
Peel off over 2mm and below 5mm: △
2mm or less peeling: ○ ↓
No peeling: ◎ (excellent)
(4) Adhesiveness after heating The inner surface of the can body subjected to the heat treatment for removing strain was washed, and after baked in an oven at 210 ° C. for 10 minutes, the degree of peeling of the resin at the tip of the can was observed. The street was evaluated. In addition, a pass is a thing of evaluation more than (circle).
Test result: peeling exceeding 10% of evaluation: xx (poor)
More than 5% but less than 10%: × ↑
Peel off over 2% and below 5%: △
2% or less peeling: ○ ↓
No peeling: ◎ (excellent)

2. Evaluation by drawing and ironing (DI molding) A DI can was manufactured as follows for a laminated metal plate using TFS having a thickness of 0.23 mm, and the suitability of the DI can was investigated.
2-1. Can making process A laminated metal plate was drawn under the following conditions and ironed to obtain a DI can.
・ First stage blank diameter: 150mm
Aperture ratio: 1.6
-Second stage aperture ratio: 1.25
-Ironing ironing punch diameter: 3-stage ironing 65.8mmφ
-Total ironing ratio of the can body 55-70% of the thickness of the laminated metal plate before forming
2-2. Distortion heat treatment The processing strain of the film introduced in the can manufacturing process was heated and held for 30 seconds in a thermal environment at a film melting point of -15 ° C and then rapidly cooled.

2-3. Evaluation of DI Can Appropriateness (1) Workability Evaluation was made as follows according to the limit that can be made without damaging the film. In addition, a pass is a thing of evaluation more than (circle).
Limiting degree of processing (total ironing rate): Molding with an evaluation total ironing rate of 55% is impossible: XX (poor)
Molding up to a total ironing rate of 55% ： × ↑
Molding up to a total ironing rate of 60%: △
Molding up to a total ironing ratio of 65%: ○ ↓
Molding up to 70% total ironing rate: ◎ (excellent)
(2) Room temperature and low temperature impact resistance evaluation After applying a neck process to a can body (total ironing rate of 65%) subjected to strain relief heat treatment, filling the can body with distilled water, attaching a lid and tightening, The bottom of the can was impacted by dropping a 0.5 kg iron ball from a height of 25 cm. Next, the lid is opened, and 1% saline solution is filled in the can so that the impacted part is immersed. After immersion for 5 minutes, a 6 V load is applied to the platinum electrode and the can metal part immersed in the solution. The current value after 5 minutes was read and evaluated as follows. The same test was performed at room temperature 20 ° C. and 0 ° C., with the former being room temperature impact resistance and the latter being low temperature impact resistance. In addition, a pass is a thing of evaluation more than (circle).
(Room temperature impact resistance evaluation)
Test result: Evaluation Current value is 30 mA or more: XX (poor)
Current value is 10 mA or more and less than 30 mA: × ↑
Current value is 5 mA or more and less than 10 mA: Δ
Current value is 1 mA to less than 5 mA: ○ ↓
Current value is less than 1 mA: ◎ (excellent)
(Low temperature impact resistance evaluation)
Test result: Evaluation Current value is 30 mA or more: Δ (poor)
Current value is 10 mA to less than 30 mA: ○ ↑
Current value is 5 mA or more and less than 10 mA: ◎
Current value is 1 mA to less than 5 mA: ◎◎ ↓
Current value is less than 1 mA: ◎ ◎ ◎ (excellent)
(3) Adhesiveness after processing The inner surface of the can body subjected to the strain relief heat treatment was washed and immersed in an aqueous solution of 1.5% by weight of citric acid-1.5% by weight of sodium chloride for 5 hours. The peeling length of the resin was observed and evaluated as follows. In addition, a pass is a thing of evaluation more than (circle).
Test result: peeling exceeding evaluation 10 mm: xx (poor)
Peel off over 5mm to 10mm: × ↑
Peel off over 2mm and below 5mm: △
2mm or less peeling: ○ ↓
No peeling: ◎ (excellent)
(4) Adhesiveness after heating The inner surface of the can body subjected to the heat treatment for removing strain was washed, and after baked in an oven at 210 ° C. for 10 minutes, the degree of peeling of the resin at the tip of the can was observed. The street was evaluated. In addition, a pass is a thing of evaluation more than (circle).
Test result: peeling exceeding 10% of evaluation: xx (poor)
More than 5% but less than 10%: × ↑
Peel off over 2% and below 5%: △
2% or less peeling: ○ ↓
No peeling: ◎ (excellent)
The survey results are shown in Tables 3 and 4.

  From Tables 1 to 4, the following can be understood for any of the can types.

  Invention Examples 1 to 5 are films in which the modified polyolefin resin defined in the present invention is dispersed in a polyester resin in which the copolymerization ratio of ethylene terephthalate and ethylene isophthalate is changed variously, and this is laminated under the lamination conditions of the present invention. Invention Examples 35 to 39 show very good moldability, impact resistance, and adhesion. Inventive Example 38 in which a film of Inventive Example 4 using a polyester resin having a low isophthalic acid content is laminated, and Inventive Example 39 in which a film of Inventive Example 5 using homopolyethylene terephthalate is further laminated has improved workability and adhesion. Although it tends to be inferior, the overall performance is good. Inventive Example 35, in which the film of Inventive Example 1 using a polyester resin having a high isophthalic acid content is laminated, has a slightly low melting point and therefore tends to be inferior in adhesion after heating, but the overall performance is good. . Furthermore, Invention Examples 33 and 34 are films using a mixture of two types of polyester resins having different copolymerization ratios within the scope of the present invention, and these were laminated under the lamination conditions of the present invention 67 and 68. Although it tends to be slightly inferior in workability, it exhibits good workability, impact resistance, and adhesion. On the other hand, Comparative Examples 1 to 6 are examples of films that do not contain a polyolefin resin in polyester resins in which the copolymerization ratios of ethylene terephthalate and ethylene isophthalate are variously changed. Comparative Examples 15-20 laminated with these films have particularly low impact resistance levels.

  Invention Examples 6 to 10 are mixed resins in which various polyolefin resins are dispersed in a polyester resin, and Invention Examples 40 to 44 obtained by laminating these resins all show good processability, impact resistance, and adhesion. Invention Example 40 in which a film of Invention Example 6 using a polyolefin resin having a slightly higher carboxylic acid-derived functional group ratio and Invention Example 44 in which a film of Invention Example 10 using a polyolefin resin having a slightly higher glass transition temperature are laminated are: There was a tendency to be slightly inferior in low temperature impact resistance. On the other hand, Comparative Examples 11 to 13 are mixed resins in which a polyolefin resin in which the ratio of the carboxylic acid-derived functional group is outside the scope of the present invention is dispersed in a polyester resin. And inferior in impact resistance.

  Comparative Example 14 is a film in which the carboxylic acid-derived group-modified polyolefin resin and the polyester resin are simply mixed. Since the modified polyolefin resin is not dispersed in the polyester resin in the form of fine particles, the comparative example 28 in which it is laminated has a workability. The impact resistance is very poor.

  Inventive Examples 11 to 18 are films in which the blending amount and the dispersion state of the modified polyolefin resin in the polyester resin are variously changed within the scope of the invention, and the Inventive Examples 45 to 45 are laminated under the laminating conditions of the present invention. 52 shows good workability, impact resistance, and adhesion. However, in Invention Example 45 in which the film of Invention Example 11 with a small amount of the modified polyolefin resin dispersed is laminated, and in Invention Example 51 in which the film of Invention Example 17 in which the number of particles of the modified polyolefin resin is very large is laminated, the low temperature resistance There is a tendency to be somewhat inferior in impact.

  On the other hand, Comparative Examples 7 to 10 are films in which the blending amount of the modified polyolefin resin in the polyester resin does not satisfy the invention, but Comparative Examples 21 to 24 laminated with the lamination conditions of the present invention are workability or resistance. Very inferior in impact. In Comparative Examples 21 and 22 in which the films of Comparative Examples 7 and 8 having a small amount of the modified polyolefin resin dispersed are laminated, the films of Comparative Examples 9 and 10 having a very low room temperature impact resistance and a large amount of the modified polyolefin resin are used. In the laminated comparative examples 23 and 24, the processability is very poor.

  Invention Examples 19 to 23 are films obtained by mixing a modified polyolefin resin and polyester resin with a titanium dioxide pigment, and Invention Examples 53 to 57 obtained by laminating these films under the lamination conditions of the present invention have good processability and impact resistance. Inventive example 53 in which the film of inventive example 19 is laminated with a pigment addition amount less than the desired range is slightly insufficient in concealing the color tone. On the other hand, Invention Example 57 obtained by laminating the film of Invention Example 23 in which the pigment addition amount is larger than the desirable range slightly reduces the workability.

  Inventive Examples 24-28 were obtained by changing the film thickness within the range of the present invention, and Inventive Examples 58-62, which were laminated under the laminating conditions of the present invention, all had good workability and impact resistance. , Showing adhesion. Inventive Examples 24 and 28 have film thicknesses exceeding the desired range of the present invention, and Inventive Examples 58 and 62 in which the films are laminated are somewhat inferior in both processability and impact resistance to those of desirable film thicknesses. .

  Inventive Examples 36 and 69 to 72 are obtained by changing the laminating conditions for the film of Inventive Example 2 within the scope of the present invention. Shows impact and adhesion. On the other hand, Comparative Example 30 was obtained by laminating the film of Inventive Example 2 under conditions lower than the lower limit of the laminating temperature range of the present invention, and evaluation was impossible because the film did not adhere to the steel plate. On the other hand, in Comparative Example 29, the film of Invention Example 2 was laminated under conditions exceeding the upper limit of the laminating temperature range of the present invention.

  Invention Examples 29 to 31 are films in which a mixed resin of the modified polyolefin resin and polyester resin of the present invention is mixed with a lubricant, a radical inhibitor, and a compatibilizer, respectively, and these are laminated under the lamination conditions of the present invention 63. -65 shows favorable workability, impact resistance, and adhesiveness. Furthermore, it has slipperiness, radical deterioration resistance, and compatibility depending on the function of the added additive. In particular, Invention Example 65 exhibits a high degree of low temperature impact resistance.

  Invention Example 32 is a film of the present invention formed by a biaxial stretching method, and Invention Examples 66 and 73 obtained by laminating the film show good performance. Inventive Example 73 has a plane orientation coefficient of 0.015 and is slightly inferior in workability. However, in a low-temperature impact resistance test, it was confirmed that it was slightly higher than that having a low plane orientation coefficient. Invention Example 66 has a plane orientation coefficient within the range of the present invention, and is extremely good in workability and impact resistance.

<Example 2>
Using a carboxylic acid-derived group-modified polyolefin resin having a primary particle size of 0.3 μm as a starting material, a polyester resin and a tumbler blender were used at a blending ratio shown in Table 5 and Table 6 and then cold blended. Was used to obtain polyester resin raw material pellets in which the modified polyolefin resin was dispersed. In the table, the resin type corresponding to the resin type code of the polyester resin and the resin type of the polyolefin resin are the same as those described in Example 1.

As in Example 1, the metal plate had a thickness of 0.18 mm for thin-walled deep drawn cans and a thickness of 0.23 mm for DI cans, all with a temper degree of DR9, a metal chromium layer of 80 mg / m ² , chromium Using tin-free steel (hereinafter abbreviated as TFS) with an oxide layer of 15 mg / m ² (converted to metal chromium), the raw resin pellets are inserted into a single screw extruder, and on one side of the metal plate, a T-die The molten resin was directly extruded and cooled once while being held in close contact with two rolls, and then immediately cooled in water immediately after laminating the resin on the opposite side by the same method to obtain a double-sided laminated metal plate. The temperature of the metal plate during lamination was 50 ° C. The lip opening width of the T die was adjusted so that the film thickness of the resin film was 6 to 55 μm. Tables 7 and 8 show the types of test resins and the resin melting temperatures during extrusion lamination. The temperature at the time of lamination is also the same as that used in Example 1 for the polyester resin and the carboxylic acid-derived group-modified polyolefin resin used.

  A modified polyolefin resin obtained by using a pelletized carboxylic acid-derived group-modified polyolefin resin as a starting material and melt-kneading at 260 ° C. directly with a polyester resin at a compounding ratio shown in Comparative Example 43 of Table 6 using a single screw extruder A mixed resin of polyester resin and polyester resin was extruded from a T die, and directly extruded to a thickness of 25 μm and laminated to the TFS.

The method for measuring the particle diameter of the modified polyolefin resin dispersed in the resin film, various temperatures in the table, and the plane orientation coefficient of the laminated metal plate are all the same as in Example 1. The laminated metal plate obtained above was processed into a thinned deep-drawn can or DI can in the same manner as in Example 1 and subjected to heat treatment for strain relief to prepare a test can. The processability, impact resistance, and adhesion of the film of the can that was made were investigated in the same manner as in Example 1.
The survey results are shown in Table 7 and Table 8.

From Tables 5 to 8, the following can be understood for any of the can types.
Inventive examples 74 to 82 are formed with a film in which the modified polyresin specified in the present invention is dispersed in a polyester resin in which the copolymerization ratio of ethylene terephthalate and ethylene isophthalate is variously changed. Shows impact resistance and adhesion. Further, Invention Example 81 using a polyester resin having a low isophthalic acid fraction and Invention Example 82 using homopolyethylene terephthalate tend to be inferior in workability and adhesion, but overall performance is good. In addition, Invention Example 74 using a polyester resin having a high isophthalic acid fraction has a slightly low melting point and thus tends to have poor adhesion after heating, but overall performance is good. Furthermore, Invention Examples 109 and 110 are obtained by mixing two types of polyester resins having different copolymerization ratios within the scope of the present invention, and have good workability and impact resistance although they tend to be slightly inferior in workability. Property and adhesion. On the other hand, Comparative Examples 31-35 are examples of resins that do not contain a polyolefin resin in polyester resins in which the copolymerization ratio of ethylene terephthalate and ethylene isophthalate is variously changed, and the level of impact resistance is particularly low.

  Invention Examples 83 to 87 are examples of mixed resins in which various polyolefin resins are dispersed in a polyester resin, and all show good processability, impact resistance, and adhesion, but a polyolefin having a slightly higher ratio of carboxylic acid-derived functional groups. Invention Example 83 using a resin and Invention Example 87 using a polyolefin resin having a slightly higher glass transition temperature tended to be slightly inferior in low-temperature impact resistance. On the other hand, Comparative Examples 40 to 42 are mixed resins in which a polyolefin resin having a carboxylic acid-derived functional group ratio outside the scope of the present invention is dispersed in a polyester resin, and all are inferior in workability and impact resistance.

  Comparative Example 43 is a resin obtained by simply mixing a carboxylic acid-derived group-modified polyolefin resin and a polyester resin, and the modified polyolefin does not disperse in the form of fine particles in the polyester resin, so that both processability and impact resistance are very poor.

  Inventive Examples 88 to 95 are resins in which the blending amount of the modified polyolefin resin in the polyester resin and the dispersion state are variously changed within the scope of the invention, and show good workability, impact resistance, and adhesion. However, the resin of Invention Example 88 in which the amount of the modified polyolefin resin to be dispersed is small and the resin of Invention Example 94 in which the number of particles of the modified polyolefin resin is very large tend to be slightly inferior in low-temperature impact resistance.

  On the other hand, Comparative Examples 36 to 39 are resins in which the blending amount of the modified polyolefin resin in the polyester resin does not satisfy the invention, but the processability or impact resistance is very poor. In Comparative Examples 36 and 37 in which the amount of the modified polyolefin resin to be dispersed is small, the impact resistance at room temperature is very inferior, and in Comparative Examples 38 and 39 in which the amount of the modified polyolefin resin is large, the workability is very inferior.

  Inventive Examples 96 to 100 are resins obtained by mixing a modified polyolefin resin and a polyester resin with a titanium dioxide pigment, exhibiting good processability, impact resistance and adhesion, and obtaining a uniform white color tone. In Invention Example 96, in which the pigment addition amount is less than the desired range, the color tone concealment is slightly insufficient. On the other hand, in the invention example 100 in which the pigment addition amount is larger than the desired range, the processability is slightly lowered.

  Invention Examples 101 to 105 are obtained by changing the film thickness of the resin within the range of the present invention, and all show good workability, impact resistance, and adhesion. In Invention Examples 101 and 105, the film thickness of the resin exceeds the desirable range of the present invention, so that both workability and impact resistance are slightly inferior to those of the desirable film thickness.

  Inventive Examples 75 to 79 are obtained by changing the extrusion laminating conditions within the scope of the present invention, and within the scope of the present invention, good workability, impact resistance and adhesion are exhibited regardless of the laminating temperature. . Invention Example 75 was laminated under conditions that were below the desirable lower limit of the lamination temperature range, and Invention Example 79 was laminated under conditions that exceeded the desirable upper limit of the lamination temperature range, both of which were workability and low-temperature impact resistance. Slightly inferior to sex.

  Invention Examples 106 to 108 are resins in which a mixed resin of the modified polyolefin resin and polyester resin of the present invention is mixed with a lubricant, a radical inhibitor, and a compatibilizing agent, and all have good processability, impact resistance, and adhesion. Indicates. Furthermore, it has slipperiness, radical degradation resistance and compatibility according to the function of the added additive, and in particular, Invention Example 108 exhibits a high degree of low temperature impact resistance.

<Example 3>
As a resin raw material, a carboxylic acid-derived group-modified polyolefin resin was cold-blended using a polyester resin and a tumbler blender at a blending ratio shown in Tables 9 to 12, and then melt-kneaded at 270 ° C. using a twin-screw extruder. A polyester resin raw material pellet in which a polyolefin resin was dispersed was obtained. The raw resin pellets are inserted into a single-screw extruder, controlled by the amount of molten resin discharged from the extruder, extruded from a multi-manifold T-die, and cooled on the rotating metal roll surface to a total thickness of 10-50 μm The resin film was continuously produced.

  On the other hand, in the case of a film having a two-layer structure, a carboxylic acid-derived group-modified polyolefin resin is cold-blended using a polyester resin and a tumbler blender at a blending ratio shown in Tables 9 to 12 as a resin raw material for the R1 layer. Polyester resin raw material pellets in which the modified polyolefin resin was dispersed were obtained by melt-kneading at 270 ° C. using an extruder. The raw material resin pellets are inserted into a single screw extruder, while a polyester resin that does not contain a modified polyolefin resin, which is a raw material for the R0 layer resin, is inserted into another single screw extruder, and the film thicknesses of the R1 layer and the R0 layer are set. While controlling by the amount of molten resin discharged from each extruder, each molten resin was introduced into a multi-manifold T-die and extruded into two layers, and a resin film was continuously produced while cooling on the surface of a rotating metal roll.

The polyester resin and carboxylic acid-derived group-modified polyolefin resin used are as follows.
1. Polyester resin (1) PET: Polyethylene terephthalate resin, intrinsic viscosity 0.62 dl / g
(2) PET / I (10): isophthalic acid copolymerized polyethylene terephthalate copolymer resin having a ratio of terephthalic acid to isophthalic acid of 90:10, intrinsic viscosity 0.62 dl / g
(3) PET / PBT (60): mixed resin having a ratio of polyethylene terephthalate to polybutylene terephthalate of 40:60, intrinsic viscosity of 0.6 dl / g
(4) PET / AD (20): adipic acid copolymerized polyethylene terephthalate copolymer resin having a ratio of terephthalic acid to adipic acid of 80:20, intrinsic viscosity of 0.6 dl / g

2. Carboxylic acid-derived group-modified polyolefin resin (1) EM1: Polymethyl methacrylate- (ethylene-ethyl acrylate copolymer) graft copolymer (Nippon Yushi Co., Ltd. Modiper A5200), weight of carboxylic acid-derived functional group Ratio 21% by weight, glass transition temperature: −30 ° C. or lower (2) EM2: polymethyl methacrylate- (ethylene-ethyl acrylate-maleic anhydride copolymer) graft copolymer (Nippon Oil & Fats Co., Ltd. Modiper A8200), 18% by weight of carboxylic acid-derived functional group, glass transition temperature: −30 ° C. or less (3) EM3: ethylene-ethyl acrylate-maleic anhydride copolymer (bondin made by Sumitomo Chemical Co., Ltd.) HX8290), weight ratio of carboxylic acid-derived functional group 11% by weight, glass transition temperature: −30 ° C. or lower (4) EM4: ethylene Crylic acid copolymer (Nucleel N1560 manufactured by Mitsui DuPont Polychemical Co., Ltd.), weight ratio of carboxylic acid-derived functional group: 8% by weight, glass transition temperature: −30 ° C. or less (5) EM5: ethylene-methacrylic acid copolymer 50% Zn neutralized product of the coalescence (Nucleal N1560 manufactured by Mitsui DuPont Polychemical Co., Ltd. partially neutralized with Zn), weight ratio of carboxylic acid-derived functional group 7% by weight, glass transition temperature: -30 ° C The following (6) EM6: 60% Zn neutralized product of ethylene-methacrylic acid copolymer (Himiran 1557 manufactured by Mitsui Dupont Polychemical Co., Ltd.), weight ratio of carboxylic acid-derived functional group 5% by weight, glass transition temperature: -30 ° C. or lower (7) EM7: ethylene-methacrylic acid copolymer (Nucrel N0200H manufactured by Mitsui Dupont Polychemical Co., Ltd.), weight of carboxylic acid-derived functional group Ratio 1% by weight, glass transition temperature: −30 ° C. or lower (8) EM8: polystyrene- (ethylene-ethyl acrylate copolymer) graft copolymer (Nippon Yushi Co., Ltd. Modiper A5100), carboxylic acid-derived functional group Group weight ratio 6% by weight, glass transition temperature: 20 ° C.
(9) EPR: ethylene-propylene rubber (EP07P manufactured by JSR Corporation), weight ratio of carboxylic acid-derived functional group 0% by weight, glass transition temperature: −30 ° C. or lower

  Further, as a resin raw material, a commercially available resin (sealer PT4274 manufactured by Mitsui DuPont Polychemical Co., Ltd.) pelletized in a state in which a commercially available carboxylic acid-derived group-modified polyolefin resin is dispersed in a polyester resin is Invention Example 32 in Table 11, Inserted as it is into a single-screw extruder at the compounding ratio shown in 36, extruded from a multi-manifold T-die while being controlled by the amount of molten resin discharged from the extruder, and cooled on the surface of a rotating metal roll, with a single layer and 2 A layered resin film was continuously produced.

The thus-obtained resin film was heated by induction heating method, tin-free steel (hereinafter abbreviated as TFS. The thickness was 0.18 mm for thin-walled deep drawn cans, and 0 for DI cans .23 mm, tempering degree DR9, metal chromium layer 80 mg / m ² , chromium oxide layer 15 mg / m ² (converted to metal chromium)), and then a laminated metal plate was obtained by a thermal bonding method in which it was quenched in water. . Tables 13 and 14 show the metal plate temperature (laminate temperature) during lamination.

  The particle diameter of the modified polyolefin resin dispersed in the R1 layer of the resin film, various temperatures in the table, and the plane orientation coefficient of the laminated metal plate were measured in the same manner as in Example 1.

  The laminated metal plate obtained above is processed into a thin-walled deep-drawn can or DI can, subjected to heat treatment for distortion, and a test can is produced. (Room temperature, low temperature), adhesion after processing, adhesion after heating, and flavor were investigated.

Details of the survey method are described below.
1. Evaluation by thinning deep drawing 1-1. Can making process A laminated metal plate was subjected to first-stage drawing and redrawing under the following conditions to obtain a thin-walled deep-drawn can.
・ First stage aperture Blank diameter ... 150-160mm
1st aperture stop: aperture ratio 1.65
-Re-drawing First re-drawing: Aperture ratio: 1.25
Second re-drawing: Aperture ratio: 1.25
Curvature radius of die corner in redrawing process: 0.4mm
Wrinkle holding weight during redrawing ... 39227N (4000kg)
-Average thinning ratio of can body 40-55% of the thickness of the laminated metal plate before molding
1-2. Distortion heat treatment The processing strain of the film introduced in the can manufacturing process was heated and held for 30 seconds in a thermal environment at a film melting point of -15 ° C and then rapidly cooled.
(1) Workability The following ratings were given according to the limit that can be processed without causing damage to the film. A pass is a thing of evaluation more than (circle).
Limiting degree of processing (thinning rate): Rating Molding rate of 40% is not possible: XX (Inferior)
Molding up to 40% thinning rate: × ↑
Moldable up to 45% thinning rate: △
Molding up to 50% thinning rate: ○ ↓
Molding up to 55% thinning rate: ◎ (excellent)
(2) Evaluation of room temperature and low temperature impact resistance After applying neck processing to a can body (thinning ratio 50%) subjected to heat treatment for removing strain, filling the can body with distilled water, attaching a lid and tightening, A 0.5 kg iron ball was dropped from a height of 30 cm onto the bottom of the can to give an impact. Next, the lid is opened, and 1% saline solution is filled in the can so that the impacted part is immersed. After immersion for 5 minutes, a 6 V load is applied to the platinum electrode and the can metal part immersed in the solution. The current value after 5 minutes was read and evaluated as follows. The same test was performed at room temperature 20 ° C. and 0 ° C., with the former being room temperature impact resistance and the latter being low temperature impact resistance. A pass is a thing of evaluation more than (circle).
(Room temperature impact resistance evaluation)
Test result: Evaluation Current value is 30 mA or more: XX (Inferior)
Current value is 10 mA or more and less than 30 mA: × ↑
Current value is 5 mA or more and less than 10 mA: Δ
Current value is 1 mA to less than 5 mA: ○ ↓
Current value is less than 1 mA: ◎ (excellent)
(Low temperature impact resistance evaluation)
Test result: Evaluation Current value is 50 mA or more: × (poor)
Current value is 30 mA to less than 50 mA: △ ↑
Current value is 10 mA or more and less than 30 mA: ○
Current value is 5 mA or more and less than 10 mA: ◎
Current value is 1 mA to less than 5 mA: ◎◎ ↓
Current value is less than 1 mA: ◎◎◎ (excellent)
(3) Adhesiveness after processing The inner surface of the can body subjected to the heat treatment for strain removal was washed and immersed in an aqueous solution of 1.5% by weight of citric acid-1.5% by weight of sodium chloride for 24 hours. The peel length of the resin was observed and evaluated. The scores are as follows. A pass is a thing of evaluation more than (circle).
Test result: peeling exceeding evaluation 10 mm: xx (poor)
Peel off over 5mm to 10mm: × ↑
Peel off over 2mm and below 5mm: △
2mm or less peeling: ○ ↓
No peeling: ◎ (excellent)
(4) Adhesiveness after heating The inner surface of the can body subjected to the heat treatment for removing strain was washed and baked in an oven at 210 ° C. for 10 minutes, and the degree of peeling of the resin at the tip of the can was observed and evaluated. . The scores are as follows. A pass is a thing of evaluation more than (circle).
Test result: peeling exceeding 10% of evaluation: xx (poor)
More than 5% but less than 10%: × ↑
Peel off over 2% and below 5%: △
Peel off over 0.5% and below 2%: ○
Less than 0.5% peeling: ◎ ↓
No peeling: ◎◎ (excellent)
(5) Flavorability After washing the inner surface of the can subjected to the strain relief heat treatment, a fragrance aqueous solution (d-limonene 20 ppm aqueous solution) is put in, sealed and left at room temperature for 20 days, then opened and driven out by ether immersion. The portion was quantified as an adsorbed amount of d-limonene per can by gas chromatography to evaluate taste characteristics. A pass is a thing of evaluation more than (circle).
Test result: Evaluation adsorption amount exceeding 200 μg / can: × (poor)
Adsorption amount exceeds 100 μg / can and below 200 μg / can: Δ ↑
Adsorption amount of 30 μg / can and 100 μg / can or less: ○
Adsorption amount 10 μg / can over 30 μg / can: ◎ ↓
Adsorption amount 10μg / can or less: ◎◎ (excellent)

2. 2. Evaluation by drawing ironing (DI molding) 2-1. Can making process A laminated metal plate was drawn under the following conditions and ironed to obtain a DI can.
・ First stage blank diameter: 150mm
Aperture ratio: 1.6
-Second stage aperture ratio: 1.25
-Ironing ironing punch diameter: 3-stage ironing 65.8mmφ
-Total ironing ratio of the can body 55-70% of the thickness of the laminated metal plate before forming
2-2. Distortion heat treatment The processing strain of the film introduced in the can manufacturing process was heated and held for 30 seconds in a thermal environment at a film melting point of -15 ° C and then rapidly cooled.
(1) Workability The following ratings were given according to the limit that can be processed without causing damage to the film. A pass is a thing of evaluation more than (circle).
Limiting degree of processing (total ironing ratio): Molding with a total ironing ratio of 55% is impossible: XX (Inferior)
Molding up to a total ironing rate of 55%: × ↑
Molding up to a total ironing rate of 60%: △
Molding up to a total ironing ratio of 65%: ○ ↓
Molding up to 70% total ironing rate: ◎ (excellent)
(2) Room temperature and low temperature impact resistance evaluation After applying a neck process to a can body (total ironing rate of 65%) subjected to strain relief heat treatment, filling the can body with distilled water, attaching a lid and tightening, The bottom of the can was impacted by dropping a 0.5 kg iron ball from a height of 25 cm. Next, the lid is opened, and 1% saline solution is filled in the can so that the impacted part is immersed. After immersion for 5 minutes, a 6 V load is applied to the platinum electrode and the can metal part immersed in the solution. The current value after 5 minutes was read and evaluated as follows. The same test was performed at room temperature 20 ° C. and 0 ° C., with the former being room temperature impact resistance and the latter being low temperature impact resistance. A pass is a thing of evaluation more than (circle).
(Room temperature impact resistance evaluation)
Test result: Evaluation Current value is 30 mA or more: XX (Inferior)
Current value is 10 mA or more and less than 30 mA: × ↑
Current value is 5 mA or more and less than 10 mA: Δ
Current value is 1 mA to less than 5 mA: ○ ↓
Current value is less than 1 mA: ◎ (excellent)
(Low temperature impact resistance evaluation)
Test result: Evaluation Current value is 50 mA or more: × (poor)
Current value is 30 mA to less than 50 mA: △ ↑
Current value is 10 mA or more and less than 30 mA: ○
Current value is 5 mA or more and less than 10 mA: ◎
Current value is 1 mA to less than 5 mA: ◎◎ ↓
Current value is less than 1 mA: ◎◎◎ (excellent)
(3) Adhesiveness after processing The inner surface of the can body subjected to the strain relief heat treatment was washed and immersed in an aqueous solution of 1.5% by weight of citric acid-1.5% by weight of sodium chloride for 5 hours. The peel length of the resin was observed and evaluated. The scores are as follows. A pass is a thing of evaluation more than (circle).
Test result: peeling exceeding evaluation 10 mm: xx (poor)
Peel off over 5mm to 10mm: × ↑
Peel off over 2mm and below 5mm: △
2mm or less peeling: ○ ↓
No peeling: ◎ (excellent)
(4) Adhesiveness after heating The inner surface of the can body subjected to the heat treatment for removing strain was washed and baked in an oven at 210 ° C. for 10 minutes, and the degree of peeling of the resin at the tip of the can was observed and evaluated. . The scores are as follows. A pass is a thing of evaluation more than (circle).
Test result: peeling exceeding 10% of evaluation: xx (poor)
More than 5% but less than 10%: × ↑
Peel off over 2% and below 5%: △
Peel off over 0.5% and below 2%: ○
Less than 0.5% peeling: ◎ ↓
No peeling: ◎◎ (excellent)
(5) Flavorability After washing the inner surface of the can subjected to the strain relief heat treatment, a fragrance aqueous solution (d-limonene 20 ppm aqueous solution) is put in, sealed and left at room temperature for 20 days, then opened and driven out by ether immersion. The portion was quantified as an adsorbed amount of d-limonene per can by gas chromatography to evaluate taste characteristics. A pass is a thing of evaluation more than (circle).
Test result: Evaluation adsorption amount exceeding 200 μg / can: × (poor)
Adsorption amount exceeds 100 μg / can and below 200 μg / can: Δ ↑
Adsorption amount of 30 μg / can and 100 μg / can or less: ○
Adsorption amount 10 μg / can over 30 μg / can: ◎ ↓
Adsorption amount 10μg / can or less: ◎◎ (excellent)
The survey results are shown in Tables 13 and 14.

  From Tables 9 to 14, the following can be understood for any of the can types.

  Invention Examples 1-3 and 5 are films in which the modified polyolefin resin defined in the present invention is dispersed in a polyester resin in which the polyester type of the mixed resin is changed in a single layer, and this is laminated under the lamination conditions of the present invention. Inventive Examples 37 to 39 and 41 exhibit very good moldability, impact resistance, adhesion, and flavor properties. Among them, in Invention Example 39 in which the film of Invention Example 3 using a polyethylene terephthalate resin copolymerized with adipic acid is laminated, the overall performance is good, but the melting point of the polyester resin is somewhat low and the barrier property is Since it is somewhat low, it tends to be inferior in adhesion and flavor after heating. In addition, Invention Examples 68 and 72 obtained by laminating Invention Examples 32 and 36 of a film produced from a resin in which a commercially available modified polyolefin resin is dispersed in a polyester resin also show good performance. On the other hand, Comparative Examples 1 to 5 are examples of films that do not contain a polyolefin resin in polyester resins with various types of polyesters. Comparative Examples 15 to 19 in which these films are laminated have particularly low levels of workability and impact resistance.

  Inventive Examples 4 to 8 are films using a mixed resin in which various polyolefin resins of the present invention are dispersed in a polyester resin, and Inventive Examples 40 to 44, which are laminated, all have good moldability and impact resistance. Inventive Example 44, which exhibited adhesion and flavor properties but was laminated with the film of Inventive Example 8 using a polyolefin resin having a slightly higher glass transition temperature, tended to be slightly inferior in workability and impact resistance. On the other hand, Comparative Examples 10 to 12 are mixed resins in which a polyolefin resin whose carboxylic acid-derived functional group ratio is outside the scope of the present invention is dispersed in a polyester resin. And inferior in impact resistance.

  Inventive Examples 9 to 16 are films in which the blending amount of the modified polyolefin resin in the polyester resin and the dispersion state were variously changed within the scope of the invention, and the inventive examples 45 to 45 were laminated under the laminating conditions of the present invention. 52 shows good workability, impact resistance, adhesion, and flavor. However, in Inventive Example 45 in which the film of Invention Example 9 having a small amount of the modified polyolefin resin dispersed is laminated and Inventive Example 51 in which the film of Invention Example 15 having a very large number of modified polyolefin resins is laminated, the impact resistance is improved. There is a tendency to be slightly inferior.

  On the other hand, Comparative Examples 6 to 9 are films in which the blending amount of the modified polyolefin resin in the polyester resin does not satisfy the present invention. However, Comparative Examples 20 to 23 in which this is laminated under the laminating conditions of the present invention are processability or Very inferior in impact resistance. In Comparative Example 20 in which the film of Comparative Example 6 having a small amount of the modified polyolefin resin to be dispersed was laminated, the impact resistance at room temperature was very poor. In Comparative Example 23 in which the film of Comparative Example 9 having a large amount of the modified polyolefin resin was laminated, The processability is very inferior.

  Inventive Examples 27 to 31 are films obtained by mixing a modified polyolefin resin and polyester resin with a titanium dioxide pigment, and Inventive Examples 63 to 67, which are laminated under the lamination conditions of the present invention, have good processability and impact resistance. Inventive example 63 in which the film of inventive example 27 is laminated with the amount of pigment added less than the desired range is slightly insufficient in concealing the color tone. It was. On the other hand, in the invention example 67 which laminated | stacked the film of the invention example 31 with more pigment addition amount than the desirable range, workability falls a little.

  Inventive Examples 17 to 21 are films in which the blending amounts of the polymerization catalyst and the antioxidant in the mixed resin were variously changed within the scope of the invention. Inventive Examples 53 to 57 were laminated under the lamination conditions of the present invention. All show good workability, impact resistance, adhesion, and flavor, but the invention example 53 with a large amount of antioxidant is slightly inferior in workability and impact resistance. On the other hand, Comparative Examples 27 and 28, in which the films of Comparative Examples 13 and 14 in which the blending amounts of the polymerization catalyst and the antioxidant in the mixed resin are out of the scope of the present invention, were laminated under the laminating conditions of the present invention, had excellent workability and resistance. Inferior in impact and adhesion.

  Inventive Examples 22 and 23 were obtained by changing the film thickness of each layer of the film, and Inventive Examples 58 and 59 obtained by laminating them under the laminating conditions of the present invention all had good workability, impact resistance, and adhesion. , Shows flavor. In Invention Example 22, since the film is slightly thin, the Invention Example 58 in which the film is laminated is slightly inferior in impact resistance.

  Inventive Examples 41 and 73 to 76 were obtained by changing the laminating conditions for the film of Inventive Example 5 within the scope of the present invention. Shows impact, adhesion, and flavor.

  Invention Examples 24 and 25 are films obtained by mixing a mixed resin of a modified polyolefin resin and a polyester resin of the present invention with a lubricant, a radical inhibitor, and a compatibilizing agent, respectively, and these were laminated under the lamination conditions of the present invention 60. , 61 all exhibit good processability, impact resistance, adhesion, and flavor properties. Furthermore, it has slipperiness, radical deterioration resistance, and compatibility depending on the function of the added additive. In particular, Invention Example 61 in which a compatibilizing agent is mixed exhibits a high degree of low temperature impact resistance.

  Invention Example 26 is a film of the present invention formed by a biaxial stretching method, and Invention Examples 62 and 77 obtained by laminating the films show good performance. Inventive Example 77 has a plane orientation coefficient of 0.015 and is slightly inferior in workability. Invention Example 62 has a plane orientation coefficient in the range of the present invention, and is extremely good in workability and impact resistance.

  Invention Examples 33 to 36 are two-layer films in which a polyester resin layer containing no olefin is provided as an upper layer, and Invention Examples 69 to 72 obtained by laminating the polyester resin layers have lower temperature impact resistance and flavor properties than single layers. Although excellent, Invention Example 71 obtained by laminating the film of Invention Example 35 using a film containing polybutylene terephthalate as an upper layer is slightly inferior in flavor property.

<Example 4>
As a resin raw material, a carboxylic acid-derived group-modified polyolefin resin was cold-blended using a polyester resin and a tumbler blender at a blending ratio shown in Tables 15 and 16, and then melt-kneaded at 270 ° C. using a twin-screw extruder for modification. A polyester resin raw material pellet in which a polyolefin resin was dispersed was obtained. Part of the resin raw material used was a resin pelletized with a commercially available carboxylic acid-derived group-modified polyolefin resin dispersed in a polyester resin (Sealer PT4274 manufactured by Mitsui Dupont Polychemical Co., Ltd.). In the table, the resin species corresponding to the resin species of the polyester resin and the resin species of the polyolefin resin are the same as those described in Example 3.

As in Example 3, the metal plate was 0.18 mm thick for thin-walled deep-drawn cans and 0.23 mm thick for DI cans, each with a tempering degree DR9, a metal chromium layer of 80 mg / m ² , chromium Using the oxide layer of 15 mg / m ² (converted to chromium metal) tin-free steel (hereinafter abbreviated as TFS), the raw material resin pellets are inserted into a single screw extruder, and in the case of two layers, the resin for the R0 layer Is inserted into another extruder and melted and extruded at the same time. The molten resin is extruded directly on one side of the metal plate and cooled once while being held in close contact with two rolls. Immediately after laminating, it was quenched in water to obtain a double-sided laminated metal plate. The temperature of the metal plate during lamination was 230 ° C. The lip opening width of the T die was adjusted so that the film thickness of the resin film was 10 to 50 μm. Tables 15 to 18 show the types of test resins and the resin melting temperatures during extrusion lamination. The polyester resin and the carboxylic acid-derived group-modified polyolefin resin used are the same as those used in Example 3.

  The particle diameter of the modified polyolefin resin dispersed in the resin film, various temperatures in the table, and the method for measuring the plane orientation coefficient of the laminated metal plate are all the same as in Example 3. The laminated metal plate obtained above was processed into a thin-walled deep-drawn can or DI can in the same manner as in Example 3 and subjected to strain relief heat treatment to prepare a test can. The processability, impact resistance, adhesion, and flavor properties of the film of the can that was made were investigated in the same manner as in Example 3.

  The survey results are shown in Tables 17 and 18.

  From Tables 15 to 18, the following can be understood for any of the can types.

  In Invention Examples 78 to 80 and 81, a resin layer in which the modified polyolefin resin defined in the present invention is dispersed in a polyester resin in which the polyester type of the mixed resin is variously formed is formed as a single layer. Shows impact resistance, adhesion, and flavor. Among them, in Invention Example 80 using a polyethylene terephthalate resin copolymerized with adipic acid, the overall performance is good, but the melting point of the polyester resin is slightly low and the barrier property is slightly low, so adhesion after heating Tend to be inferior in flavor and flavor. Inventive Examples 108 and 112 produced from a resin in which a commercially available modified polyolefin resin is dispersed in a polyester resin also show good performance. On the other hand, Comparative Examples 29 to 32 are examples of resins that do not contain a polyolefin resin in polyester resins in which various types of polyesters are changed. These have a particularly low level of workability and impact resistance.

  Inventive Examples 81-85 use a mixed resin in which various polyolefin resins of the present invention are dispersed in a polyester resin, and all show good moldability, impact resistance, adhesion, and flavor properties. Invention Example 85 using a polyolefin resin having a slightly higher glass transition temperature tended to be slightly inferior in workability and impact resistance. On the other hand, Comparative Examples 37 to 39 are mixed resins in which a polyolefin resin having a carboxylic acid-derived functional group ratio outside the scope of the present invention is dispersed in a polyester resin, and all are inferior in workability and impact resistance.

  Invention Examples 86 to 93 are obtained by laminating mixed resins in which the amount of the modified polyolefin resin in the polyester resin and the dispersion state are variously changed within the scope of the invention under the extrusion lamination conditions of the present invention. Good workability, impact resistance, adhesion and flavor. However, Invention Example 86 with a small amount of the modified polyolefin resin dispersed and Invention Example 92 (93) with a very large number of modified polyolefin resins tend to be slightly inferior in impact resistance.

  On the other hand, Comparative Examples 33 to 36 are resin layers in which the blending amount of the modified polyolefin resin in the polyester resin does not satisfy the invention, but the processability or impact resistance is very poor. In Comparative Example 33 in which the amount of the modified polyolefin resin to be dispersed is small, the impact resistance at room temperature is very poor, and in Comparative Example 36 in which the amount of the modified polyolefin resin is large, the workability is very poor. Further, in Comparative Examples 35 and 36 in which the amount of the modified polyolefin resin is large, there is a problem with the flavor.

  Inventive Examples 103 to 107 are mixed resin layers obtained by mixing a modified polyolefin resin and a polyester resin with a titanium dioxide pigment, exhibiting good processability, impact resistance, adhesion, and flavor, and having a uniform white color. Although color tone can be obtained, Invention Example 103 in which the pigment addition amount is less than the desired range has slightly lacked the color tone concealment. On the other hand, in the invention example 107 where the pigment addition amount is larger than the desired range, the processability is slightly lowered.

  Invention Examples 94 to 98 are resin layers in which the blending amounts of the polymerization catalyst and the antioxidant in the mixed resin are variously changed within the scope of the invention, and all have good workability, impact resistance, adhesion, and flavor properties. As shown, Invention Example 94 with a large amount of antioxidant is slightly inferior in workability and impact resistance. On the other hand, Comparative Examples 40 and 41 in which the blending amounts of the polymerization catalyst and the antioxidant in the mixed resin are out of the scope of the invention are inferior in workability, impact resistance, and adhesion.

  Invention Examples 99 and 100 were obtained by changing the film thickness of the resin layer, and all exhibited good processability, impact resistance, adhesion, and flavor. Inventive Example 99 is slightly inferior in impact resistance since the resin layer is slightly thin.

  Invention Examples 101 and 102 are resin layers in which a mixed resin of the modified polyolefin resin and polyester resin of the present invention is mixed with a lubricant, a radical inhibitor, and a compatibilizer, respectively, and all have good processability, impact resistance, and adhesion. Shows sexuality and flavor. Furthermore, it has slipperiness, radical deterioration resistance, and compatibility depending on the function of the added additive. In particular, Invention Example 102 containing a compatibilizing agent exhibits a high degree of low temperature impact resistance.

  Invention Examples 109 to 112 are two-layer resins in which an olefin-free polyester resin layer is provided as an upper layer, and are superior in low-temperature impact resistance and flavor compared to a single layer, but include resins containing polybutylene terephthalate in the upper layer. Inventive Example 111 using the above is slightly inferior in flavor.

<Example 5>
As a raw material for the R1 layer, a carboxylic acid-derived group-modified polyolefin resin having a primary particle size of 0.3 μm is cold-blended using a polyester resin and a tumbler blender at a blending ratio shown in Tables 19 and 20, and then biaxial. Polyester resin raw material pellets in which the modified polyolefin resin was dispersed were obtained by melt-kneading at 270 ° C. using an extruder. The raw material resin pellets are inserted into a single screw extruder, while a polyester resin that does not contain a modified polyolefin resin, which is a raw material for the R0 layer resin, is inserted into another single screw extruder, and the film thicknesses of the R1 layer and the R0 layer are set. While controlling by the amount of molten resin discharged from each extruder, each molten resin is introduced into a multi-manifold T-die, extruded into two layers, cooled on the rotating metal roll surface, and a total of 9.5 to 70 μm. A resin film having a thickness was continuously produced.

The polyester resin and carboxylic acid-derived group-modified polyolefin resin used are as follows.
1. Polyester resin (1) PET / PBT (90): mixed resin having a ratio of polyethylene terephthalate (EFG10 manufactured by Kanebo Synthetic Co., Ltd.) and polybutylene terephthalate (Planac manufactured by Dainippon Ink & Chemicals, Inc.), intrinsic viscosity 0.6 dl / g, Tg 27 ° C., Tc 60 ° C., Tm 215 ° C., Ge content 10 ppm
(2) PET / PBT (80): a mixed resin having a ratio of polyethylene terephthalate (EFG10 manufactured by Kanebo Synthetic Co., Ltd.) and polybutylene terephthalate (Planac manufactured by Dainippon Ink & Chemicals, Inc.) of 20:80, inherent viscosity of 0. 6dl / g, Tg35 ° C, Tc75 ° C, Tm220 ° C, Ge content 10ppm
(3) PET / PBT (70): a mixed resin in which the ratio of polyethylene terephthalate (EFG10 manufactured by Kanebo Gosei Co., Ltd.) and polybutylene terephthalate (Planac manufactured by Dainippon Ink & Chemicals, Inc.) is 30:70. 62 dl / g, Tg 45 ° C., Tc 90 ° C., Tm 230 ° C., Ge content 20 ppm
(4) PET / PBT (60): a mixed resin having a ratio of polyethylene terephthalate (EFG10 manufactured by Kanebo Synthetic Co., Ltd.) and polybutylene terephthalate (Planac manufactured by Dainippon Ink & Chemicals, Inc.) having an intrinsic viscosity of 0. 6dl / g, Tg50 ° C, Tc105 ° C, Tm235 ° C, Ge content 10ppm
(5) PET / PBT (40): a mixed resin having a ratio of polyethylene terephthalate (EFG10 manufactured by Kanebo Synthetic Co., Ltd.) and polybutylene terephthalate (Planac manufactured by Dainippon Ink & Chemicals, Inc.) having an intrinsic viscosity of 0. 6dl / g, Tg60 ° C, Tc120 ° C, Tm240 ° C, Ge content 10ppm
(6) PET / PBT (20): a mixed resin having a ratio of polyethylene terephthalate (EFG10 manufactured by Kanebo Synthetic Co., Ltd.) and polybutylene terephthalate (Planac manufactured by Dainippon Ink & Chemicals, Inc.) of 80:20; 6dl / g, Tg65 ° C, Tc140 ° C, Tm245 ° C, Ge content 10ppm
(7) PET: Polyethylene terephthalate resin (EFG10 manufactured by Kanebo Gosei Co., Ltd.), intrinsic viscosity 0.62 dl / g, Tg 72 ° C., Tc 150 ° C., Tm 255 ° C., Ge content 20 ppm
(8) PET / I (10): ethylene phthalate-ethylene isophthalate copolymer resin (IP121B manufactured by Kanebo Gosei Co., Ltd.) having a ratio of terephthalic acid to isophthalic acid of 90:10, intrinsic viscosity 0.6 dl / g, Tg 70 ° C., Tc 170 ° C., Tm 230 ° C., Ge content 10 ppm.

2. Carboxylic acid-derived group-modified polyolefin resin (1) EM1: Polymethyl methacrylate- (ethylene-ethyl acrylate copolymer) graft copolymer (Nippon Yushi Co., Ltd. Modiper A5200), weight of carboxylic acid-derived functional group Ratio 21% by weight, glass transition temperature: −30 ° C. or lower (2) EM2: polymethyl methacrylate- (ethylene-ethyl acrylate-maleic anhydride copolymer) graft copolymer (Nippon Oil & Fats Co., Ltd. Modiper A8200), 18% by weight of carboxylic acid-derived functional group, glass transition temperature: −30 ° C. or less (3) EM3: ethylene-ethyl acrylate-maleic anhydride copolymer (bondin made by Sumitomo Chemical Co., Ltd.) HX8290), weight ratio of carboxylic acid-derived functional group 11% by weight, glass transition temperature: −30 ° C. or lower (4) EM4: ethylene Crylic acid copolymer (Nucleel N1560 manufactured by Mitsui DuPont Polychemical Co., Ltd.), weight ratio of carboxylic acid-derived functional group: 8% by weight, glass transition temperature: −30 ° C. or less (5) EM5: ethylene-methacrylic acid copolymer 50% Zn neutralized product of the coalescence (Nucleal N1560 manufactured by Mitsui DuPont Polychemical Co., Ltd. partially neutralized with Zn), weight ratio of carboxylic acid-derived functional group 7% by weight, glass transition temperature: -30 ° C The following (6) EM6: 60% Zn neutralized product of ethylene-methacrylic acid copolymer (Himiran 1557 manufactured by Mitsui Dupont Polychemical Co., Ltd.), weight ratio of carboxylic acid-derived functional group 5% by weight, glass transition temperature: -30 ° C. or lower (7) EM7: ethylene-methacrylic acid copolymer (Nucrel N0200H manufactured by Mitsui Dupont Polychemical Co., Ltd.), weight of carboxylic acid-derived functional group Ratio 1% by weight, glass transition temperature: −30 ° C. or lower (8) EM8: polystyrene- (ethylene-ethyl acrylate copolymer) graft copolymer (Nippon Yushi Co., Ltd. Modiper A5100), carboxylic acid-derived functional group Group weight ratio 6% by weight, glass transition temperature: 20 ° C.
(9) EPR: ethylene-propylene rubber (EP07P manufactured by JSR Corporation), weight ratio of carboxylic acid-derived functional group 0% by weight, glass transition temperature: −30 ° C. or lower.

  As the R1 layer resin raw material, the pelletized carboxylic acid-derived group-modified polyolefin resin and the polyester resin are directly inserted into a single-screw extruder at the blending ratio shown in Comparative Example 16 of Table 20, while the R0 layer resin raw material is obtained. The polyester resin not containing the modified polyolefin resin is inserted into another single-screw extruder, and the thickness of the R1 layer and the R0 layer is controlled by the amount of molten resin discharged from each extruder, A resin film having a total thickness of 9.5 to 70 μm was continuously produced while being introduced into a manifold-type T-die, extruded into two layers, and cooled on the surface of a rotating metal roll.

The thus-obtained resin film was heated by induction heating method, tin-free steel (hereinafter abbreviated as TFS. The thickness was 0.18 mm for thin-walled deep drawn cans, and 0 for DI cans .23 mm, tempering degree DR9, metal chromium layer 80 mg / m ² , chromium oxide layer 15 mg / m ² (converted to metal chromium)), and then a laminated metal plate was obtained by a thermal bonding method in which it was quenched in water. . Tables 21 and 22 show the metal plate temperature (laminate temperature) during lamination.

  The particle diameter of the modified polyolefin resin dispersed in the R1 layer of the resin film, various temperatures in the table, and the plane orientation coefficient of the laminated metal plate were measured in the same manner as in Example 1.

  The laminated metal plate obtained above was processed into a thin-walled deep-drawn can or DI can, and subjected to heat treatment for removing strain to prepare a test can. The processability, impact resistance (room temperature, low temperature), adhesion after processing, adhesion after heating, and retort treatment were investigated for canned can bodies. The retort treatment property was evaluated by the cloudiness (white turbidity resistance) of the film on the bottom of the can after the retort treatment. The lid was obtained by subjecting a laminated metal plate to the same processing as that of a commercially available 250 ml negative pressure can (3-piece can).

Details of the survey method are described below.
1. Evaluation by thinning deep drawing 1-1. Can making process A laminated metal plate was subjected to first-stage drawing and redrawing under the following conditions to obtain a thin-walled deep-drawn can.
・ First stage aperture Blank diameter ... 150-160mm
1st aperture stop: aperture ratio 1.65
-Re-drawing First re-drawing: Aperture ratio: 1.25
Second re-drawing: Aperture ratio: 1.25
Curvature radius of die corner in redrawing process: 0.4mm
Wrinkle holding weight during redrawing ... 39227N (4000kg)
-Average thinning ratio of can body 40-55% of the thickness of the laminated metal plate before molding
1-2. Distortion heat treatment The processing strain of the film introduced in the can manufacturing process was heated and held for 30 seconds in a thermal environment at a film melting point of -15 ° C and then rapidly cooled.
(1) Workability The following ratings were given according to the limit that can be processed without causing damage to the film. A pass is a thing of evaluation more than (circle).
Limiting degree of processing (thinning rate): Rating Molding rate of 40% is not possible: XX (Inferior)
Molding up to 40% thinning rate: × ↑
Moldable up to 45% thinning rate: △
Molding up to 50% thinning rate: ○ ↓
Molding up to 55% thinning rate: ◎ (excellent)
(2) Evaluation of room temperature and low temperature impact resistance After applying neck processing to a can body (thinning ratio 50%) subjected to heat treatment for removing strain, filling the can body with distilled water, attaching a lid and tightening, A 0.5 kg iron ball was dropped from a height of 30 cm onto the bottom of the can to give an impact. Next, the lid is opened, and 1% saline solution is filled in the can so that the impacted part is immersed. After immersion for 5 minutes, a 6 V load is applied to the platinum electrode and the can metal part immersed in the solution. The current value after 5 minutes was read and evaluated as follows. The same test was performed at room temperature 20 ° C. and 0 ° C., with the former being room temperature impact resistance and the latter being low temperature impact resistance. A pass is a thing of evaluation more than (circle).
(Room temperature impact resistance evaluation)
Test result: Evaluation Current value is 30 mA or more: XX (Inferior)
Current value is 10 mA or more and less than 30 mA: × ↑
Current value is 5 mA or more and less than 10 mA: Δ
Current value is 1 mA to less than 5 mA: ○ ↓
Current value is less than 1 mA: ◎ (excellent)
(Low temperature impact resistance evaluation)
Test result: Evaluation Current value is 50 mA or more: × (poor)
Current value is 30 mA to less than 50 mA: △ ↑
Current value is 10 mA or more and less than 30 mA: ○
Current value is 5 mA or more and less than 10 mA: ◎
Current value is 1 mA to less than 5 mA: ◎◎ ↓
Current value is less than 1 mA: ◎ ◎ ◎ (excellent)
(3) Adhesiveness after processing The inner surface of the can body subjected to the heat treatment for strain removal was washed and immersed in an aqueous solution of 1.5% by weight of citric acid-1.5% by weight of sodium chloride for 24 hours. The peel length of the resin was observed and evaluated. The scores are as follows. A pass is a thing of evaluation more than (circle).
Test result: peeling exceeding evaluation 10 mm: xx (poor)
Peel off over 5mm to 10mm: × ↑
Peel off over 2mm and below 5mm: △
2mm or less peeling: ○ ↓
No peeling: ◎ (excellent)
(4) Adhesiveness after heating The inner surface of the can body subjected to the heat treatment for removing strain was washed and baked in an oven at 210 ° C. for 10 minutes, and the degree of peeling of the resin at the tip of the can was observed and evaluated. . The scores are as follows. A pass is a thing of evaluation more than (circle).
Test result: peeling exceeding 10% of evaluation: xx (poor)
More than 5% but less than 10%: × ↑
Peel off over 2% and below 5%: △
Peel off over 0.5% and below 2%: ○
Less than 0.5% peeling: ◎ ↓
No peeling: ◎◎ (excellent)
(5) Cloudiness of the film after retorting treatment The can body (thinning ratio: 50%) subjected to heat treatment for removing strain is subjected to neck processing, filled with distilled water, attached with a lid, wound and cooled to 4 ° C. Thereafter, a retort treatment was performed in an atmosphere at 130 ° C. for 1 hour. The degree to which the film on the bottom of the can became clouded after the retort treatment was visually observed. A pass is a thing of evaluation more than (circle).
Test result: White turbidity exceeding 50% of the entire evaluation: × (poor)
White turbidity exceeds 10% and 50% or less: △ ↑
White turbidity exceeds 2% of total and 10% or less: ○
There is very little cloudiness (less than 2% of the total): ◎ ↓
No change: ◎◎ (excellent)

2. 2. Evaluation by drawing ironing (DI molding) 2-1. Can making process A laminated metal plate was drawn under the following conditions and ironed to obtain a DI can.
・ First stage blank diameter: 150mm
Aperture ratio: 1.6
-Second stage aperture ratio: 1.25
-Ironing ironing punch diameter: 3-stage ironing 65.8mmφ
-Total ironing ratio of the can body 55-70% of the thickness of the laminated metal plate before forming
1-2. Distortion heat treatment The processing strain of the film introduced in the can manufacturing process was heated and held for 30 seconds in a thermal environment at a film melting point of -15 ° C and then rapidly cooled.
(1) Workability The following ratings were given according to the limit that can be processed without causing damage to the film. A pass is a thing of evaluation more than (circle).
Limiting degree of processing (total ironing ratio): Molding with a total ironing ratio of 55% is impossible: XX (poor)
Molding up to a total ironing rate of 55% ： × ↑
Molding up to a total ironing rate of 60%: △
Molding up to a total ironing ratio of 65%: ○ ↓
Molding up to 70% total ironing rate: ◎ (excellent)
(2) Room temperature and low temperature impact resistance evaluation After applying a neck process to a can body (total ironing rate of 65%) subjected to strain relief heat treatment, filling the can body with distilled water, attaching a lid and tightening, The bottom of the can was impacted by dropping a 0.5 kg iron ball from a height of 25 cm. Next, the lid is opened, and 1% saline solution is filled in the can so that the impacted part is immersed. After immersion for 5 minutes, a 6 V load is applied to the platinum electrode and the can metal part immersed in the solution. The current value after 5 minutes was read and evaluated as follows. The same test was performed at room temperature 20 ° C. and 0 ° C., with the former being room temperature impact resistance and the latter being low temperature impact resistance. A pass is a thing of evaluation more than (circle).
(Room temperature impact resistance evaluation)
Test result: Evaluation Current value is 30 mA or more: XX (poor)
Current value is 10 mA or more and less than 30 mA: × ↑
Current value is 5 mA or more and less than 10 mA: Δ
Current value is 1 mA to less than 5 mA: ○ ↓
Current value is less than 1 mA: ◎ (excellent)
(Low temperature impact resistance evaluation)
Test result: Evaluation Current value is 50 mA or more: × (poor)
Current value is 30 mA to less than 50 mA: △ ↑
Current value is 10 mA or more and less than 30 mA: ○
Current value is 5 mA or more and less than 10 mA: ◎
Current value is 1 mA to less than 5 mA: ◎◎ ↓
Current value is less than 1 mA: ◎ ◎ ◎ (excellent)
(3) Adhesiveness after processing The inner surface of the can body subjected to the strain relief heat treatment was washed and immersed in an aqueous solution of 1.5% by weight of citric acid-1.5% by weight of sodium chloride for 5 hours. The peel length of the resin was observed and evaluated. The scores are as follows. A pass is a thing of evaluation more than (circle).
Test result: peeling exceeding evaluation 10 mm: xx (poor)
Peel off over 5mm to 10mm: × ↑
Peel off over 2mm and below 5mm: △
2mm or less peeling: ○ ↓
No peeling: ◎ (excellent)
(4) Adhesiveness after heating The inner surface of the can body subjected to the heat treatment for removing strain was washed and baked in an oven at 210 ° C. for 10 minutes, and the degree of peeling of the resin at the tip of the can was observed and evaluated. . The scores are as follows. A pass is a thing of evaluation more than (circle).
Test result: peeling exceeding 10% of evaluation: xx (poor)
More than 5% but less than 10%: × ↑
Peel off over 2% and below 5%: △
Peel off over 0.5% and below 2%: ○
Less than 0.5% peeling: ◎ ↓
No peeling: ◎◎ (excellent)
(5) Turbidity of film after retort treatment (anti-turbidity)
A can body (total ironing rate 65%) subjected to heat treatment for strain relief is subjected to neck processing, filled with distilled water, covered with a lid, tightened, cooled to 4 ° C, and then in an atmosphere at 130 ° C for 1 hour Retort treatment was performed. The degree to which the film on the bottom of the can became clouded after the retort treatment was visually observed. A pass is a thing of evaluation more than (circle).
Test result: White turbidity exceeding 50% of the entire evaluation: × (poor)
White turbidity exceeds 10% and 50% or less: △ ↑
White turbidity exceeds 2% of total and 10% or less: ○
There is very little cloudiness (less than 2% of the total): ◎ ↓
No change: ◎◎ (excellent)
The survey results are shown in Tables 21 and 22.

  From Tables 19 to 22, the following can be understood for any of the can types.

  Invention Examples 1 to 7 are resin layers in which the modified polyolefin resin defined in the present invention is dispersed in a polyester resin in which the R1 layer has various mixing ratios of polyethylene terephthalate and polybutylene terephthalate, and the R0 layer is defined in the present invention. Inventive Examples 38 to 44, which are terephthalate films and laminated under the laminating conditions of the present invention, exhibit very good moldability, impact resistance, adhesion, and white turbidity resistance. Among them, in Inventive Example 43 in which the film of Inventive Example 6 using a polyester resin having a low polybutylene terephthalate ratio is laminated, and in Inventive Example 44 in which the film of Inventive Example 7 using homopolyethylene terephthalate is laminated, in Polybutylene terephthalate The lower the ratio, the poorer the adhesion after heating and the white turbidity resistance after retorting, but the overall performance is still good. Inventive Example 45, in which the film of Invention Example 8 using polyethylene terephthalate copolymerized with isophthalic acid copolymerized polyester resin of R1 layer, tends to be slightly inferior in adhesion after heating and anti-turbidity after retorting. There is still good overall performance. On the other hand, Invention Examples 38 and 39 obtained by laminating the films of Invention Examples 1 and 2 having a very high polybutylene terephthalate ratio tend to be inferior in adhesion after heating because the melting point is somewhat low, but overall performance is good. It is. On the other hand, Comparative Examples 1 to 8 are examples of films that do not contain a polyolefin resin in a polyester resin in which the mixing ratio of polyethylene terephthalate and polybutylene terephthalate is variously changed. Comparative Examples 23 to 30 in which these films are laminated have particularly low impact resistance levels.

  Inventive Examples 9 to 13 are films using a mixed resin in which various polyolefin resins are dispersed in a polyester resin for the R1 layer, and Inventive Examples 46 to 50, which are laminated, all have good moldability and impact resistance. Inventive Example 46 in which the film of Inventive Example 9 using a polyolefin resin having a slightly higher ratio of carboxylic acid-derived functional groups, showing adhesion and white turbidity resistance, and an invention using a polyolefin resin having a slightly higher glass transition temperature Invention Example 50 in which the film of Example 13 was laminated tended to be slightly inferior in low-temperature impact resistance. On the other hand, Comparative Examples 13 to 15 are mixed resins in which a polyolefin resin in which the ratio of the carboxylic acid-derived functional group is outside the scope of the present invention is dispersed in a polyester resin. And inferior in impact resistance.

  Comparative Example 16 is a film in which the carboxylic acid-derived group-modified polyolefin resin and the polyester resin are simply mixed. Since the modified polyolefin resin is not dispersed in the polyester resin in the form of fine particles, the comparative example 38 in which it is laminated has processability. The impact resistance is very poor.

  Invention Examples 14 to 21 are films in which the blending amount of the modified polyolefin resin in the polyester resin and the dispersion state are variously changed within the scope of the invention. 58 shows good workability, impact resistance, adhesion, and cloudiness resistance. However, in Invention Example 51 in which the film of Invention Example 14 with a small amount of the modified polyolefin resin dispersed is laminated, and in Invention Example 57 in which the film of Invention Example 20 in which the number of modified polyolefin resins is very large is laminated, the impact resistance at low temperature is low. There is a tendency to be slightly inferior in sex.

  On the other hand, Comparative Examples 9 to 12 are films in which the blending amount of the modified polyolefin resin in the polyester resin does not satisfy the invention, but Comparative Examples 31 to 34, which are laminated under the lamination conditions of the present invention, have workability or resistance. Very inferior in impact. In Comparative Examples 31 and 32 in which the films of Comparative Examples 9 and 10 having a small amount of the modified polyolefin resin to be dispersed are laminated, the films of Comparative Examples 11 and 12 having a large amount of the modified polyolefin resin are very inferior in impact resistance at room temperature. In the laminated comparative examples 33 and 34, the processability is very poor.

  Invention Examples 33 to 37 are films obtained by mixing a modified polyolefin resin and polyester resin with a titanium dioxide pigment, and Invention Examples 70 to 74 obtained by laminating them under the lamination conditions of the present invention have good processability and impact resistance. Inventive Example 70 in which the film of Inventive Example 33 laminated with a less amount of pigment added than the desired range is slightly lacking in concealment of color tone. It was. On the other hand, in the invention example 74 which laminated | stacked the film of the invention example 37 with more pigment addition amount than the desirable range, workability falls a little.

  Inventive Examples 22 to 28 are obtained by changing the film thickness of each layer of the film within the scope of the present invention. Inventive Examples 59 to 65 obtained by laminating the layers under the laminating conditions of the present invention all have good processability and resistance. Shows impact, adhesion, and cloudiness resistance. Inventive Examples 22 and 28 have an overall film thickness exceeding the desired range of the present invention, and thus Inventive Examples 59 and 65 in which the films are laminated have both processability and impact resistance compared to those of the desired film thickness. Somewhat inferior. On the other hand, the inventive examples 17a to 20a are the film thicknesses of the respective layers of the film, or the inventive examples 39a to 42a obtained by laminating them with a film whose film thickness ratio is outside the desirable range of the present invention, compared with the inventive examples 22 to 28, Slightly inferior in balance between workability and impact resistance.

  Inventive Examples 41 and 75 to 78 were obtained by changing the laminating conditions for the film of Inventive Example 4 within the scope of the present invention. Shows impact, adhesion, and cloudiness resistance. On the other hand, Comparative Example 39 was obtained by laminating the film of Inventive Example 4 under conditions lower than the lower limit of the laminating temperature range of the present invention, and evaluation was impossible because the film did not adhere to the steel plate. On the other hand, in Comparative Example 40, the film of Invention Example 4 was laminated under conditions exceeding the upper limit of the laminating temperature range of the present invention.

  Invention Examples 29 to 31 are films obtained by mixing a mixed resin of a modified polyolefin resin and a polyester resin of the present invention with a lubricant, a radical inhibitor, and a compatibilizing agent, respectively, and were laminated under the lamination conditions of the present invention 66. -68 show favorable workability, impact resistance, adhesion, and cloudiness resistance. Furthermore, it has slipperiness, radical deterioration resistance, and compatibility according to the function of the added additive. In particular, Invention Example 68 exhibits a high degree of low temperature impact resistance.

  Invention Example 32 is a film of the present invention formed by a biaxial stretching method, and Invention Examples 69 and 79 obtained by laminating the films show good performance. Inventive Example 79 has a plane orientation coefficient of 0.015 and is slightly inferior in workability. Invention Example 69 has a plane orientation coefficient in the range of the seventh invention, and is extremely good in workability and impact resistance.

  Invention Examples 21a and 22a are films using a polyester resin other than the present invention in the R0 layer, and Invention Examples 43a and 44a obtained by laminating the films are slightly inferior in adhesion after heating.

<Example 6>
Using a carboxylic acid-derived group-modified polyolefin resin having a primary particle size of 0.3 μm as a starting material, a polyester resin and a tumbler blender were used at a blending ratio shown in Tables 23 to 24, and then a twin-screw extruder was used. It was melt kneaded at 260 ° C. to obtain polyester resin raw material pellets in which the modified polyolefin resin was dispersed. In the table, the resin types corresponding to the codes of the polyester resin type and the polyolefin resin type are the same as those described in Example 5.

As in Example 5, the metal plate was 0.18 mm thick for thin-walled deep-drawn cans and 0.23 mm thick for DI cans, both tempering DR9, metal chromium layer 80 mg / m ² , chromium Using an oxide layer of 15 mg / m ² (converted to chromium metal) tin-free steel (hereinafter abbreviated as TFS), the raw resin pellets are inserted into a single screw extruder to form a resin for the R1 layer, and for the R0 layer. Is inserted into another extruder, melted and extruded at the same time, put into one T die with a combining adapter, and the molten resin in two layers is extruded directly on one side of the metal plate and sandwiched between two rolls After being cooled once while being in close contact, immediately after laminating the resin on the opposite side by the same method, it was quenched in water to obtain a double-sided laminated metal plate. The temperature of the metal plate during lamination was 230 ° C. The lip opening width of the T die was adjusted so that the film thickness of the resin film was 9.5 to 70 μm. Tables 23 to 24 also show the types of test resins and the resin melting temperatures during extrusion lamination. The temperature during lamination is also the same as that used in Example 5 for the polyester resin and carboxylic acid-derived group-modified polyolefin resin used.

  A modified polyolefin resin obtained by using a pelletized carboxylic acid-derived group-modified polyolefin resin as a starting material and melt-kneading at 265 ° C. using a single-screw extruder as it is with a compounding ratio shown in Comparative Example 61 of Table 25 A mixed resin of polyester resin and polyester resin was extruded from a T die to form an R1 layer, and the laminate was directly extruded to a thickness of 26 μm on the TFS.

The particle diameter of the modified polyolefin resin dispersed in the resin film, various temperatures in the table, and the method for measuring the plane orientation coefficient of the laminated metal plate are all the same as in Example 5. The laminated metal plate obtained above was processed into a thin-walled deep-drawn can or DI can in the same manner as in Example 5 and subjected to strain relief heat treatment to produce a test can. The processability, impact resistance, adhesion, and retortability of the can-made can body were investigated in the same manner as in Example 5.
The survey results are shown in Tables 25 and 26.

  From Tables 23 to 26, the following can be understood for any of the can types.

  In Invention Examples 80 to 90, a film using a resin layer in which a modified polyolefin resin defined in the present invention is dispersed in a polyester resin in which the ratio of polyethylene terephthalate and polybutylene terephthalate is changed is used for the R1 layer. Also exhibits good processability, impact resistance, adhesion, and white turbidity resistance. Among them, in Invention Example 89 using a polyester resin having a low polybutylene terephthalate ratio, and in Invention Example 90 using homopolyethylene terephthalate, the lower the polybutylene terephthalate ratio, the higher the adhesion after heating and the resistance to retort treatment. Although it tends to be inferior in cloudiness, the overall performance is still good. Inventive Example 91 using polyethylene terephthalate copolymerized with polyester resin of R1 layer with isophthalic acid tends to be slightly inferior in adhesion after heating and anti-turbidity after retorting, but still overall performance Is good. On the other hand, Invention Examples 80 and 81 having a very high polybutylene terephthalate ratio tend to be inferior in adhesion after heating because of their slightly lower melting points, but overall performance is good. On the other hand, Comparative Examples 47 to 53 are examples in which a polyolefin resin is not included in a polyester resin in which the mixing ratio of polyethylene terephthalate and polybutylene terephthalate is variously changed, but the level of impact resistance is particularly low.

  Inventive Examples 91 to 96 are mixed resins in which various polyolefin resins are dispersed in a polyester resin, and are used for the R1 layer, and all show good moldability, impact resistance, adhesion, and cloudiness resistance. Inventive Example 92 using a polyolefin resin having a slightly higher carboxylic acid-derived functional group ratio and Inventive Example 96 using a polyolefin resin having a slightly higher glass transition temperature tended to be slightly inferior in low-temperature impact resistance. On the other hand, Comparative Examples 58-60 are mixed resins in which a polyolefin resin having a carboxylic acid-derived functional group ratio outside the scope of the present invention is dispersed in a polyester resin, and all are inferior in workability and impact resistance.

  Comparative Example 61 is a resin obtained by simply mixing a carboxylic acid-derived group-modified polyolefin resin and a polyester resin, and the modified polyolefin resin does not disperse in a fine particle form in the polyester resin, so that both processability and impact resistance are very poor. .

  Invention Examples 97 to 104 are resins in which the blending amount of the modified polyolefin resin in the polyester resin and the dispersion state are variously changed within the scope of the invention, but good workability, impact resistance, adhesion, and cloudiness resistance Showing gender. However, Invention Example 97 in which the amount of the modified polyolefin resin to be dispersed is small and Invention Example 103 in which the number of the modified polyolefin resin is very large tend to be slightly inferior in low-temperature impact resistance.

  On the other hand, Comparative Examples 54 to 57 are resins whose blending amount of the modified polyolefin resin in the polyester resin does not satisfy the invention, but are very inferior in processability or impact resistance. In Comparative Examples 54 and 55 in which the amount of the modified polyolefin resin to be dispersed is small, the impact resistance at room temperature is very poor, and in Comparative Examples 56 and 57 in which the amount of the modified polyolefin resin is large, the workability is very inferior.

  Invention Examples 115 to 119 are resins obtained by mixing a modified polyolefin resin and a polyester resin with a titanium dioxide pigment, exhibiting good processability, impact resistance, adhesion, and white turbidity resistance, and having a uniform white color tone However, in Example 115 where the pigment addition amount is less than the desired range, the concealment of the color tone is slightly insufficient. On the other hand, in the invention example 119 in which the pigment addition amount is larger than the desirable range, the processability is slightly lowered.

  Inventive Examples 105 to 111 are obtained by changing the film thickness of each layer of the film within the range of the present invention, and all exhibit good processability, impact resistance, adhesion, and cloudiness resistance. Inventive Examples 105 and 111 are slightly inferior in workability and impact resistance to those having a desirable film thickness because the total film thickness of the film exceeds the desirable range of the present invention. On the other hand, Invention Examples 120 to 123 were laminated with a resin whose film thickness ratio or film thickness ratio was outside the desirable range of the present invention, so that the balance between workability and impact resistance was compared with Invention Examples 105 to 111. Slightly inferior.

  Invention Examples 112 to 114 are resins obtained by mixing a lubricant, a radical inhibitor, and a compatibilizing agent with the mixed resin of the modified polyolefin resin and the polyester resin of the present invention, and all have good processability, impact resistance, and adhesion. It shows white turbidity resistance. Furthermore, it has slipperiness, radical deterioration resistance, and compatibility depending on the function of the added additive, and in particular, Invention Example 114 exhibits a high degree of low temperature impact resistance.

  Invention Examples 124 and 125 are resins using a polyester resin other than the present invention for the R0 layer, and are slightly inferior in adhesion after heating.

<Example 7>
As a raw material for the R1 layer, a carboxylic acid-derived group-modified polyolefin resin is cold-blended using a polyester resin and a tumbler blender at a compounding ratio shown in Tables 27 to 29, and then melt-kneaded at 270 ° C. using a twin-screw extruder. Thus, a polyester resin raw material pellet in which the modified polyolefin resin was dispersed was obtained. The raw material resin pellets are inserted into a single screw extruder, while the modified polyolefin resin that is the R2 layer resin raw material is inserted into another single screw extruder, and the film thicknesses of the R1 layer and the R2 layer are determined from the respective extruders. Each molten resin was introduced into a multi-manifold T-die and extruded into two layers while being controlled by the amount of molten resin discharged, and a resin film was continuously produced while cooling on the rotating metal roll surface.

  Further, in the case of a three-layer structure having an R0 layer, a polyester resin as a raw material for the R0 layer is further inserted into another single-screw extruder, and the thicknesses of the R0 layer, R1 layer, and R2 layer are set to the respective extruders. Each molten resin was introduced into a multi-manifold T-die and extruded into three layers while being controlled by the amount of molten resin discharged from the resin, and a resin film was continuously produced while cooling on the rotating metal roll surface.

The polyester resin and carboxylic acid-derived group-modified polyolefin resin used are as follows.
1. Polyester resin (1) PET: Polyethylene terephthalate resin, intrinsic viscosity 0.62 dl / g
(2) PET / I: isophthalic acid copolymerized polyethylene terephthalate resin having a ratio of terephthalic acid to isophthalic acid of 90:10, intrinsic viscosity of 0.62 dl / g
(3) PET / PBT: mixed resin having a ratio of polyethylene terephthalate to polybutylene terephthalate of 40:60, intrinsic viscosity of 0.6 dl / g
(4) PET / AD: adipic acid copolymerized polyethylene terephthalate resin having a ratio of terephthalic acid to adipic acid of 80:20, intrinsic viscosity of 0.6 dl / g

2. Carboxylic acid-derived group-modified polyolefin resin (1) EM1: Polymethyl methacrylate- (ethylene-ethyl acrylate copolymer) graft copolymer (Nippon Yushi Co., Ltd. Modiper A5200), Carboxylic acid-derived functional group carboxyl Acid conversion weight ratio: 21% by weight, glass transition temperature: −30 ° C. or lower (2) EM2: polymethyl methacrylate- (ethylene-ethyl acrylate-maleic anhydride copolymer) graft copolymer (Nippon Yushi Co., Ltd.) Modiper A8200), carboxylic acid-derived functional group weight ratio of 18% by weight, glass transition temperature: −30 ° C. or less (3) EM3: ethylene-ethyl acrylate-maleic anhydride copolymer (Sumitomo Chemical Co., Ltd.) Bondin HX8290 manufactured by Co., Ltd.) Carboxylic acid derived functional group weight ratio of 11% by weight, glass transition temperature : -30 ° C. or lower (4) EM4: ethylene-methacrylic acid copolymer (Nucleel N1560 manufactured by Mitsui Dupont Polychemical Co., Ltd.), carboxylic acid equivalent weight ratio of carboxylic acid-derived functional group, 8% by weight, glass transition temperature: -30 ° C. or lower (5) EM5: 50% Zn neutralized product of ethylene-methacrylic acid copolymer (neutralized by Mitsui DuPont Polychemical Co., Ltd. Nucleol N1560 with Zn), carboxylic acid-derived functional group Carboxylic acid equivalent weight ratio of 7% by weight, glass transition temperature: -30 ° C. or lower (6) EM6: 60% Zn neutralized product of ethylene-methacrylic acid copolymer (High Milan 1557 manufactured by Mitsui Dupont Polychemical Co., Ltd.) ), 5% by weight of carboxylic acid-derived functional group in terms of carboxylic acid, glass transition temperature: −30 ° C. or lower (7) EM7: ethylene-methacrylic acid copolymer (Nucleel N0200H manufactured by Mitsui DuPont Polychemical Co., Ltd.), carboxylic acid-derived functional group weight ratio of 1% by weight, glass transition temperature: −30 ° C. or less (8) EM8: polystyrene- (ethylene-ethyl acrylate) Copolymer) Graft copolymer (Nippon Yushi Co., Ltd. Modiper A5100), carboxylic acid-derived functional group weight ratio of 6% by weight, glass transition temperature: 20 ° C
(9) EPR: ethylene-propylene rubber (EP07P manufactured by JSR Corporation), carboxylic acid-derived functional group weight ratio of 0% by weight, glass transition temperature: −30 ° C. or less

  Furthermore, as a resin raw material, commercially available resin (sealer PT4274 manufactured by Mitsui DuPont Polychemical Co., Ltd.) pelletized in a state in which a commercially available carboxylic acid-derived group-modified polyolefin resin is dispersed in a polyester resin, Invention Example 41 in Table 28, 46, the modified polyolefin resin, which is the R2 layer resin raw material, is inserted into another single screw extruder, and the thicknesses of the R1 layer and the R2 layer are respectively extruded. While controlling by the amount of molten resin discharged from the machine, each molten resin was introduced into a multi-manifold T-die and extruded into two layers, and a resin film was continuously produced while cooling on the rotating metal roll surface. In the case of a three-layer structure having an R0 layer, a polyester resin, which is an R0 layer resin raw material, is further inserted into another single-screw extruder, and the film thicknesses of the R0 layer, R1 layer, and R2 layer are determined from the respective extruders. While controlling by the amount of molten resin discharged, each molten resin was introduced into a multi-manifold T-die and extruded into three layers, and a resin film was continuously produced while cooling on the surface of a rotating metal roll.

The resin film thus obtained was thermocompression bonded to both surfaces of tin-free steel (hereinafter abbreviated as TFS) heated by an induction heating method, and then a laminated metal plate was obtained by a thermal bonding method in which the resin film was quenched in water. Tables 30 and 31 show the metal plate temperature (laminate temperature) during lamination. The TFS plate thickness is 0.18 mm for thin-walled deep-drawn cans and 0.23 mm for DI cans, and the tempering degree is DR9. The adhesion amounts are 80 mg / m ² and 15 mg / m ² (in terms of chromium metal), respectively.

  The particle diameter of the modified polyolefin resin dispersed in the R1 layer of the resin film, various temperatures in the table, and the plane orientation coefficient of the laminated metal plate were measured in the same manner as in Example 1.

  Further, the laminated metal plate obtained above is processed into a thin-walled deep-drawn can or DI can, subjected to heat treatment for distortion, and a test can is produced. Impact properties (room temperature, low temperature), adhesion after processing, adhesion after heating, and flavor were investigated.

  Details of the survey method are described below.

1. Evaluation by thinning deep drawing 1-1. Can making process A laminated metal plate was subjected to first-stage drawing and redrawing under the following conditions to obtain a thin-walled deep-drawn can.
・ First stage aperture Blank diameter ... 150-160mm
1st aperture stop: aperture ratio 1.65
-Re-drawing First re-drawing: Aperture ratio: 1.25
Second re-drawing: Aperture ratio: 1.25
Curvature radius of die corner in redrawing process: 0.4mm
Wrinkle holding weight during redrawing: 39227N (4000kg)
-Average thinning ratio of can body 45 to 60% of the thickness of the laminated metal plate before forming
1-2. Distortion heat treatment The processing strain of the film introduced in the can manufacturing process was heated and held for 30 seconds in a thermal environment at a film melting point of -15 ° C and then rapidly cooled.
(1) Workability The following ratings were given according to the limit that can be processed without causing damage to the film. A pass is a thing of evaluation more than (circle).
Limiting degree of processing (thinning ratio): Molding with an evaluation thinning ratio of 45% is impossible: XX (Inferior)
Molding up to 45% thinning rate: × ↑
Moldable up to 50% thinning rate: △
Molding up to 55% thinning rate: ○ ↓
Molding up to 60% thinning rate: ◎ (excellent)
(2) Evaluation of room temperature and low temperature impact resistance After applying neck processing to the can body (thinning ratio 55%) subjected to heat treatment for removing strain, filling the can body with distilled water, attaching a lid and tightening, A 0.5 kg iron ball was dropped from a height of 30 cm onto the bottom of the can to give an impact. Next, the lid is opened, and 1% saline solution is filled in the can so that the impacted part is immersed. After immersion for 5 minutes, a 6 V load is applied to the platinum electrode and the can metal part immersed in the solution. The current value after 5 minutes was read and evaluated as follows. The same test was performed at room temperature 20 ° C. and 0 ° C., with the former being room temperature impact resistance and the latter being low temperature impact resistance. A pass is a thing of evaluation more than (circle).
(Room temperature impact resistance evaluation)
Test result: Evaluation Current value is 3 mA or more: XX (Inferior)
Current value is 1 mA to less than 3 mA: × ↑
Current value of 0.5 mA to less than 1 mA: Δ
Current value is 0.1 mA to less than 0.5 mA: ○ ↓
Current value is less than 0.1 mA: ◎ (excellent)
(Low temperature impact resistance evaluation)
Test result: Evaluation Current value is 5 mA or more: × (Inferior)
Current value is 3 mA or more and less than 5 mA: △ ↑
Current value of 1 mA to less than 3 mA: ○
Current value of 0.5 mA to less than 1 mA: ◎
Current value is 0.1 mA to less than 0.5 mA: ◎◎ ↓
Current value is less than 0.1 mA: ◎◎◎ (excellent)
(3) Adhesiveness after processing The inner surface of the can body subjected to the heat treatment for strain removal was washed and immersed in an aqueous solution of 1.5% by weight of citric acid-1.5% by weight of sodium chloride for 24 hours. The peel length of the resin was observed and evaluated. The scores are as follows. A pass is a thing of evaluation more than (circle).
Test result: Evaluation exceeds 5 mm: xx (poor)
Peel off over 2mm and below 5mm: × ↑
Exfoliation exceeding 1 mm and 2 mm or less: △
1mm or less peeling: ○ ↓
No peeling: ◎ (excellent)
(4) Adhesiveness after heating The inner surface of the can body subjected to the heat treatment for removing strain was washed and baked in an oven at 210 ° C. for 10 minutes, and the degree of peeling of the resin at the tip of the can was observed and evaluated. . The scores are as follows. A pass is a thing of evaluation more than (circle).
Test result: Evaluation exceeds 5%: x (poor)
Peel off over 2% and below 5%: △ ↑
1% to 2% or less: ○
1% or less peeling: ◎ ↓
No peeling: ◎◎ (excellent)
(5) Flavorability After washing the inner surface of the can subjected to the strain relief heat treatment, a fragrance aqueous solution (d-limonene 20 ppm aqueous solution) is put in, sealed and left at room temperature for 20 days, then opened and driven out by ether immersion. The portion was quantified as an adsorbed amount of d-limonene per can by gas chromatography to evaluate taste characteristics. A pass is a thing of evaluation more than (circle).
Test result: Evaluation adsorption amount exceeding 200 μg / can: × (poor)
Adsorption amount exceeds 100 μg / can and below 200 μg / can: Δ ↑
Adsorption amount of 30 μg / can and 100 μg / can or less: ○
Adsorption amount 10 μg / can over 30 μg / can: ◎ ↓
Adsorption amount 10μg / can or less: ◎◎ (excellent)

2. 2. Evaluation by drawing ironing (DI molding) 2-1. Can making process A laminated metal plate was drawn under the following conditions and ironed to obtain a DI can.
・ First stage blank diameter: 150mm
Aperture ratio: 1.6
-Second stage aperture ratio: 1.25
-Ironing ironing punch diameter: 3-stage ironing 65.8mmφ
-Total ironing ratio of the can body 60-75% of the thickness of the laminated metal plate before forming
2-2. Distortion heat treatment The processing strain of the film introduced in the can manufacturing process was heated and held for 30 seconds in a thermal environment at a film melting point of -15 ° C and then rapidly cooled.
(1) Workability The following ratings were given according to the limit that can be processed without causing damage to the film. A pass is a thing of evaluation more than (circle).
Limiting degree of processing (total ironing ratio): Molding with a total ironing ratio of 60% is impossible: XX (poor)
Molding up to 60% total ironing rate: × ↑
Molding up to a total ironing rate of 65%: △
Molding up to 70% total ironing rate: ○ ↓
Molding up to 75% total ironing rate: ◎ (excellent)
(2) Room temperature and low-temperature impact resistance evaluation After applying a neck process to a can body (total ironing rate 70%) subjected to strain relief heat treatment, filling the can body with distilled water, attaching a lid and tightening, The bottom of the can was impacted by dropping a 0.5 kg iron ball from a height of 25 cm. Next, the lid is opened, and 1% saline solution is filled in the can so that the impacted part is immersed. After immersion for 5 minutes, a 6 V load is applied to the platinum electrode and the can metal part immersed in the solution. The current value after 5 minutes was read and evaluated as follows. The same test was performed at room temperature 20 ° C. and 0 ° C., with the former being room temperature impact resistance and the latter being low temperature impact resistance. A pass is a thing of evaluation more than (circle).
(Room temperature impact resistance evaluation)
Test result: Evaluation Current value is 3 mA or more: XX (Inferior)
Current value is 1 mA to less than 3 mA: × ↑
Current value of 0.5 mA to less than 1 mA: Δ
Current value is 0.1 mA to less than 0.5 mA: ○ ↓
Current value is less than 0.1 mA: ◎ (excellent)
(Low temperature impact resistance evaluation)
Test result: Evaluation Current value is 5 mA or more: × (Inferior)
Current value is 3 mA or more and less than 5 mA: △ ↑
Current value of 1 mA to less than 3 mA: ○
Current value of 0.5 mA to less than 1 mA: ◎
Current value is 0.1 mA to less than 0.5 mA: ◎◎ ↓
Current value is less than 0.1 mA: ◎◎◎ (excellent)
(3) Adhesiveness after processing The inner surface of the can body subjected to the strain relief heat treatment was washed and immersed in an aqueous solution of 1.5% by weight of citric acid-1.5% by weight of sodium chloride for 5 hours. The peel length of the resin was observed and evaluated. The scores are as follows. A pass is a thing of evaluation more than (circle).
Test result: Evaluation exceeds 5 mm: xx (poor)
Peel off over 2mm and below 5mm: × ↑
Exfoliation exceeding 1 mm and 2 mm or less: △
1mm or less peeling: ○ ↓
No peeling: ◎ (excellent)
(4) Adhesiveness after heating The inner surface of the can body subjected to the heat treatment for removing strain was washed and baked in an oven at 210 ° C. for 10 minutes, and the degree of peeling of the resin at the tip of the can was observed and evaluated. . The scores are as follows. A pass is a thing of evaluation more than (circle).
Test result: Evaluation exceeds 5%: x (poor)
Peel off over 2% and below 5%: △ ↑
1% to 2% or less: ○
1% or less peeling: ◎ ↓
No peeling: ◎◎ (excellent)
(5) Flavorability After washing the inner surface of the can subjected to the strain relief heat treatment, a fragrance aqueous solution (d-limonene 20 ppm aqueous solution) is put in, sealed and left at room temperature for 20 days, then opened and driven out by ether immersion. The portion was quantified as an adsorbed amount of d-limonene per can by gas chromatography to evaluate taste characteristics. A pass is a thing of evaluation more than (circle).
Test result: Evaluation adsorption amount exceeding 200 μg / can: × (poor)
Adsorption amount exceeds 100 μg / can and below 200 μg / can: Δ ↑
Adsorption amount of 30 μg / can and 100 μg / can or less: ○
Adsorption amount 10 μg / can over 30 μg / can: ◎ ↓
Adsorption amount 10μg / can or less: ◎◎ (excellent)
The survey results are shown in Tables 30 and 31.

  From Tables 27 to 31, the following can be understood for any of the can types.

  Invention Examples 1-4 are mixed resin layers in which the modified polyolefin resin defined in the present invention is dispersed in various polyester resins in the R1 layer, and the film using the modified polyolefin resin layer defined in the present invention in the R2 layer. Inventive Examples 47 to 50, which are laminated on the metal plate of the present invention, exhibit good processability, impact resistance, adhesion, and flavor properties. Among them, in Invention Example 49 using polyethylene terephthalate resin copolymerized with adipic acid, the overall performance is good, but the melting point of the polyester resin is slightly low and the barrier property is slightly low, so that adhesion after heating Tend to be low in strength and flavor. In addition, Invention Example 87 obtained by laminating Invention Example 41 of a film manufactured from a resin in which a commercially available modified polyolefin resin is dispersed in a polyester resin also shows good performance. On the other hand, Comparative Examples 1 to 5 are examples of films that do not contain the modified polyolefin resin defined in the present invention in polyester resins in which polyester types are variously changed. Comparative Examples 20-24 in which these films are laminated have particularly low levels of workability and impact resistance.

  Inventive Examples 4 to 10 are films using a mixed resin in which various modified polyolefin resins defined in the present invention are dispersed in a polyester resin. Inventive Examples 50 to 56, which are laminated, all have good processability. Films of Invention Examples 4 and 6 to 8 using modified polyolefin resins that exhibit impact resistance, adhesion, and flavor properties, but have an appropriate amount of carboxylic acid-derived functional groups and a glass transition temperature of −30 ° C. or lower. Inventive Examples 50 and 52 to 54 in which La is laminated are excellent in all of workability, impact resistance, adhesion, and flavor. On the other hand, Comparative Example 6 is a film in which a mixed resin obtained by dispersing a polyolefin resin having no carboxylic acid-derived functional group in a polyester resin is used for the R1 layer, and Comparative Example 25 in which this is laminated is processability and impact resistance. Very inferior.

  Invention Examples 11 to 18 are films in which the blending amount of the modified polyolefin resin dispersed in the polyester resin of the R1 mixed resin layer and the dispersion state are variously changed within the scope of the present invention. The laminated invention examples 57 to 64 all show good processability, impact resistance, adhesion, and flavor, but the amount of modified polyolefin resin to be dispersed is particularly appropriate, and the number of particles per fixed volume is also appropriate. Invention Examples 58 and 60 to 61 obtained by laminating the films of Invention Examples 12 and 14 to 15 are excellent in all of workability, impact resistance, adhesion, and flavor properties.

  On the other hand, Comparative Examples 7 to 10 are films in which the blending amount of the modified polyolefin resin in the polyester resin of the R1 mixed resin layer does not satisfy the present invention, but Comparative Examples 26 to 29 in which these are laminated are all processable. Or it is very inferior in impact resistance. In Comparative Example 26 in which the film of Comparative Example 7 having a small number of dispersed modified polyolefin resin particles is laminated and Comparative Example 29 in which the film of Comparative Example 10 having a large number of modified polyolefin resin particles is laminated, workability and impact resistance Very inferior.

  Inventive Examples 19 to 25 were obtained by changing the film thicknesses of the R1 layer and R2 layer of the film within the range specified in the present invention. , Impact resistance, adhesion, and flavor, among which the R1 layer to R2 layer thickness ratio is in the range of 5 to 10, and the R1 layer thickness is in the range of 15 to 25 μm. Invention Examples 66 to 67 and 69 obtained by laminating Invention Examples 20 to 21 and 23 are excellent in all of workability, impact resistance, adhesion, and flavor. Inventive Example 13a is a film in which the thickness ratio R1 / R2 of the mixed resin layer of R1 and the modified polyolefin layer of R2 is smaller than the desirable range of the present invention. Compared to 71, the mechanical performance of the film and adhesion to the underlying metal plate are slightly inferior. On the other hand, Invention Example 14a is a film in which R1 / R2 is larger than the preferred range of the present invention. Inventive Example 33a laminated therewith is slightly more adhesive to the base metal plate than Inventive Examples 65-71. Inferior.

  Invention Examples 26 to 31 are films using various modified polyolefin resins defined in the present invention for the R2 layer, and Invention Examples 72 to 77 obtained by laminating these films all have good processability, impact resistance and adhesion. Inventive Examples 73 to 75 in which films of Inventive Examples 27 to 29 using a modified polyolefin resin having a flavor property but having an appropriate amount of carboxylic acid-derived functional groups and having a glass transition temperature of −30 ° C. or lower are laminated. Excellent in processability, impact resistance, adhesion, and flavor. On the other hand, Comparative Example 13 is a film using a polyolefin resin having no carboxylic acid-derived functional group for the R2 layer, and Comparative Example 32 in which this is laminated is very inferior in workability and impact resistance.

  Invention Examples 32-34 are films in which the modified polyolefin resin and polyester resin of the present invention are mixed with a lubricant, a radical inhibitor, and a compatibilizer, respectively. Good workability, impact resistance, adhesion and flavor. Furthermore, it has slipperiness, radical deterioration resistance, and compatibility according to the function of the added additive, and in Example 80 in which a compatibilizer is mixed, a high degree of low temperature impact resistance is manifested.

  Invention Example 35 is a film of the present invention formed by a biaxial stretching method, and Invention Examples 81 and 97 obtained by laminating the films show good performance. Inventive Example 97 has a plane orientation coefficient of 0.015 and tends to be slightly inferior in workability, but Inventive Example 81 has a plane orientation coefficient in the range of the present invention, and has a level of impact resistance. high.

  Invention Examples 36 to 40 are films in which a titanium dioxide pigment is mixed with the film of the present invention, and Invention Examples 82 to 86 obtained by laminating the films show good processability, impact resistance, adhesion, and flavor properties. A white uniform color tone can be obtained, but in the invention example 82 in which the film of the invention example 36 in which the pigment addition amount is less than the desired range is laminated, the concealment of the color tone is slightly insufficient. On the other hand, in the invention example 86 in which the film of the invention example 40 having a pigment addition amount larger than the desired range is laminated, the processability is slightly lowered.

  Inventive Examples 93 to 96 were obtained by changing the laminating conditions for the film of Inventive Example 4 within the scope of the present invention, but within the scope of the present invention, good workability and impact resistance were obtained regardless of the laminating temperature. , Shows adhesion and flavor.

  Invention Examples 42 to 46 are three-layer films obtained by laminating an olefin-free polyester resin R0 layer, a mixed resin layer R1 layer, and a modified polyolefin layer R2 layer (lamination of the R0 layer on the R1 layer). Inventive Examples 88 to 92 are very excellent in all of workability, impact resistance, adhesion, and flavor properties. In particular, a polyester resin layer made of polyethylene terephthalate or isophthalic acid copolymerized polyethylene terephthalate is used as the R0 layer. Inventive Examples 88 to 89 and 92 in which the film used in thickness is laminated are very excellent in low-temperature impact resistance and flavor.

  Invention Examples 15a and 16a are three-layer films in which a polyester resin R0 layer not containing olefin, a mixed resin layer R1 layer, and a modified polyolefin layer R2 layer are laminated (the R0 layer is laminated on the R1 layer). The invention examples 34a and 35a laminated with the invention, which are out of the preferred range of the present invention, are inferior in adhesion to the invention examples 42 to 46 in which the R2 layer is within the preferred range of the present invention.

<Example 8>
As a resin raw material for the R1 layer, a carboxylic acid-derived group-modified polyolefin resin is cold-blended using a polyester resin and a tumbler blender at a compounding ratio shown in Tables 32-34, and then melt-kneaded at 270 ° C. using a twin-screw extruder. Thus, a polyester resin raw material pellet in which the modified polyolefin resin was dispersed was obtained. In the table, the resin type corresponding to the resin type code of the polyester resin and the resin type of the polyolefin resin are the same as those described in Example 7. Also, as a part of the resin material for R1 layer, a commercially available resin (sealer PT4274 manufactured by Mitsui Dupont Polychemical Co., Ltd.) in which the carboxylic acid-derived group-modified polyolefin resin is dispersed in a polyester resin is used as it is. Using.

As in Example 7, the metal plate had a thickness of 0.18 mm for a thin-walled deep-drawn can and a thickness of 0.23 mm for a DI can, and both had a temper DR9 and a metal chromium layer of 80 mg / m ^2. Using a TFS with a chromium oxide layer of 15 mg / m ² (in terms of chromium metal), the R1 layer raw material resin pellets are inserted into a single screw extruder, and in the case of two layers, a modified polyolefin resin that becomes the R2 layer resin raw material is used. Insert each melted resin into a multi-manifold T-die while controlling the film thickness of the R1 layer and R2 layer by the amount of molten resin discharged from each extruder into two layers. Extrude, extrude the molten resin directly on one side of the metal plate that has been heated to 230 ° C in advance, cool it while sandwiching it between two rolls, and then laminate the resin on the opposite side in the same way Immediately after this, it was quenched in water to obtain a double-sided laminated metal plate.

  Further, in the case of a three-layer structure having R0 layers, a polyester resin as a R0 layer resin raw material is further inserted into another single screw extruder, and the film thicknesses of the R0 layer, R1 layer, and R2 layer are determined from the respective extruders. Each molten resin is introduced into a multi-manifold T-die and extruded in three layers while being controlled by the amount of molten resin discharged, and two molten resins are extruded directly onto one side of the metal plate heated to 230 ° C. in advance. The sheet was cooled once while being held in close contact with each other, and immediately after laminating the resin on the opposite side by the same method, it was quenched in water to obtain a double-sided laminated metal plate.

  The lip opening width of the T die was adjusted so that the film thickness of the resin film was as shown in Tables 32-34. Tables 32-37 show the types of the test resins and the resin melting temperatures during extrusion lamination. The polyester resin and carboxylic acid-derived group-modified polyolefin resin used are the same as those used in Example 7.

  The particle diameter of the modified polyolefin resin dispersed in the resin film, various temperatures in the table, and the method for measuring the plane orientation coefficient of the laminated metal plate are all the same as in Example 7. The laminated metal plate obtained above was processed into a thin-walled deep-drawn can or DI can in the same manner as in Example 7 and subjected to strain relief heat treatment to prepare a test can. The processability, impact resistance, adhesion, and flavor properties of the can-made can bodies were investigated in the same manner as in Example 7.

  The survey results are shown in Tables 35-37.

  From Tables 32-37, the following can be understood for any of the can types.

  Invention Examples 98 to 101 are mixed resin layers in which the modified polyolefin resin defined in the present invention is dispersed in various polyester resins in the R1 layer, and the laminate using the modified polyolefin resin layer defined in the present invention is also used in the R2 layer. It is a steel plate and exhibits good workability, impact resistance, adhesion, and flavor. Among them, in Invention Example 100 using a polyethylene terephthalate resin copolymerized with adipic acid, the overall performance is good, but the melting point of the polyester resin is somewhat low and the barrier property is slightly low, so adhesion after heating Tend to be low in strength and flavor. In addition, Invention Example 137 of a laminated steel sheet produced from a resin in which a commercially available modified polyolefin resin is dispersed in a polyester resin also exhibits good performance. On the other hand, Comparative Examples 39 to 42 are examples of laminated steel sheets that do not contain the modified polyolefin resin defined in the present invention in polyester resins in which the polyester types are variously changed, and the levels of workability and impact resistance are particularly low.

  Invention Examples 101 to 107 are examples of laminated steel sheets using a mixed resin in which various modified polyolefin resins defined in the present invention are dispersed in a polyester resin, all having good workability, impact resistance, adhesion, Inventive examples 101 and 103 to 105 using a modified polyolefin resin having a flavor property but having an appropriate amount of a carboxylic acid-derived functional group and having a glass transition temperature of −30 ° C. or lower are workability, impact resistance, Excellent adhesion. On the other hand, Comparative Example 43 is an example in which a mixed resin in which a polyolefin resin having no carboxylic acid-derived functional group is dispersed in a polyester resin is used for the R1 layer, and is extremely inferior in workability and impact resistance.

  Invention Examples 108 to 115 are laminated steel sheets in which the blending amount of the modified polyolefin resin dispersed in the polyester resin of the R1 mixed resin layer and the dispersion state are variously changed within the scope of the present invention, and all have good processing. Inventive Examples 109, 111, and 112, which show properties, impact resistance, and adhesion, but have an appropriate amount of the modified polyolefin resin to be dispersed and a suitable number of particles per volume, workability, impact resistance, Excellent in adhesion and flavor.

  On the other hand, Comparative Examples 44 to 47 are examples in which the blending amount of the modified polyolefin resin in the polyester resin of the R1 mixed resin layer does not satisfy the present invention, but all are extremely inferior in workability or impact resistance. In Comparative Example 44 in which the amount of the modified polyolefin resin to be dispersed is small and Comparative Example 47 in which the amount of the modified polyolefin resin is large, the processability and impact resistance are very poor.

  Inventive Examples 116 to 122 are obtained by changing the film thicknesses of the R1 layer and the R2 layer within the range specified in the present invention, and all show good workability, impact resistance, adhesion, and flavor properties. In particular, Invention Examples 117, 118, and 120, in which the thickness ratio R1 / R2 of the R1 layer and the R2 layer is in the range of 5 to 10 and the thickness of the R1 layer is in the range of 15 to 25 μm, Excellent impact, adhesion and flavor. Inventive example 143 is an example in which the thickness ratio R1 / R2 of the R1 layer and the R2 layer is smaller than the preferred range of the present invention. Slightly inferior in adhesion to the plate. On the other hand, Invention Example 144 is an example in which R1 / R2 is larger than the preferred range of the present invention, but is slightly inferior in adhesion to the base metal plate as compared with Invention Examples 116-122.

  Invention Examples 123 to 128 are laminated steel sheets using various modified polyolefin resins defined in the present invention for the R2 layer, and all show good workability, impact resistance, adhesion, and flavor properties. Invention Examples 124 to 126 using modified polyolefin resins having an appropriate amount of acid-derived functional groups and having a glass transition temperature of −30 ° C. or less are excellent in all of workability, impact resistance, adhesion, and flavor properties.

  Invention Examples 129 to 131 are laminated steel sheets in which a mixed resin of the modified polyolefin resin and polyester resin of the present invention is mixed with a lubricant, a radical inhibitor, and a compatibilizing agent, all having good workability, impact resistance, and adhesion. Shows sexuality and flavor. Furthermore, it has slipperiness, radical deterioration resistance, and compatibility depending on the function of the added additive, and in particular, Invention Example 131 in which a compatibilizing agent is mixed exhibits a high degree of low temperature impact resistance.

  Invention Examples 132 to 136 are laminated steel sheets in which a titanium dioxide pigment is mixed with the resin layer of the present invention, exhibiting good processability, impact resistance, adhesion, and obtaining a uniform white color tone. In the invention example 132 in which the amount is less than the desired range, the color tone concealment is slightly insufficient. On the other hand, in Invention Example 136 in which the pigment addition amount is larger than the desired range, the processability is slightly lowered.

  Inventive examples 138 to 142 are steel sheets obtained by laminating a three-layer resin in which a polyester resin layer (R0 layer) not further containing olefin is provided on the R1 layer, and have workability, impact resistance, adhesion, and flavor properties. Although all are very excellent, Invention Examples 138, 139, and 142 of laminated steel sheets using a polyester resin layer made of polyethylene terephthalate or an isophthalic acid copolymerized polyethylene terephthalate specified in the present invention as an R0 layer in an appropriate film thickness. Has excellent low temperature impact resistance and flavor.

  Inventive Examples 145 and 146 are steel plates obtained by laminating a three-layer resin in which a polyester resin layer (R0 layer) not further containing olefin is provided on the R1 layer, but the thickness ratio R1 / R2 between the R1 layer and the R2 layer is Since it deviates from the preferred range of the present invention, the adhesion is inferior as compared with Invention Examples 138 to 142.

Claims (37)

In a thermoplastic polyester resin, it consists of a mixed resin in which a granular resin mainly present in a granular state with a particle diameter of 0.1 to 5 μm is dispersed in a range of 3 to 30% by weight in the total resin, The granular resin is a modified polyolefin resin containing a functional group derived from carboxylic acid in a weight ratio of 2 to 20% by weight in terms of carboxylic acid. The modified polyolefin resin is characterized in that the amount of the modified polyolefin resin present in the film in a granular state with a particle diameter of 0.1 to 5 μm is in the range of 3 to 25 vol% in terms of the volume fraction in the mixed resin. The resin film for metal plate lamination according to claim 1. 3. The resin film for metal plate lamination according to claim 1, wherein the thermoplastic polyester resin is a polyester having polyethylene terephthalate and / or isophthalic acid copolymerized polyethylene terephthalate as a main basic skeleton. 4. The ratio of the terephthalic acid of the dicarboxylic acid component which comprises the said thermoplastic polyester resin, and isophthalic acid is 97: 3-85: 15 by molar ratio, The description in any one of Claims 1-3 characterized by the above-mentioned. Resin film for laminating metal plates. The main monomer component constituting the thermoplastic polyester resin is that the dicarboxylic acid is terephthalic acid, the diol component is ethylene glycol and 1,4-butanediol, and the ratio is 20:80 to 80:20 in molar ratio. The resin film for laminating a metal plate according to any one of claims 1 to 4, wherein the resin film is laminated. 6. The metal according to claim 1, wherein the ratio X / Y of the polyester polymerization catalyst amount X and the antioxidant amount Y in the mixed resin is 0.2 or more by weight ratio. Resin film for laminate. The antioxidant film content in the said mixed resin is 500 ppm or less, The resin film for metal plate laminations in any one of Claims 1-6 characterized by the above-mentioned. The resin film for metal plate lamination according to any one of claims 1 to 7, wherein the resin film contains a pigment in an amount of 5 to 40% by weight. The resin film for metal plate lamination according to any one of claims 1 to 8, wherein the resin film has a thickness of 10 to 50 µm. A resin layer R1 layer composed of the mixed resin according to any one of claims 1 to 8 and a polyester resin layer R0 layer mainly composed of polyethylene terephthalate copolymerized with polyethylene terephthalate and / or isophthalic acid are laminated. A resin film for laminating a metal plate, which is a film having a structure and designed so that the R0 layer becomes an outermost layer when laminated on a metal plate. The thickness of the R1 layer is 10 to 50 μm, the thickness of the R0 layer is 1 to 10 μm, and the thickness ratio R1 / R0 between the R1 layer and the R0 layer is R1 / R0 = 2/1 to 10/1. The resin film for laminating a metal plate according to claim 10, wherein the resin film is a laminate. A structure in which a resin layer R1 layer made of the mixed resin according to any one of claims 1 to 8 and a resin layer R2 layer mainly composed of a modified polyolefin resin having a functional group derived from a carboxylic acid are laminated. A resin film for laminating a metal plate, wherein the R2 layer is designed to come into contact with the metal plate when laminated on the metal plate. The thickness of the R1 layer is 10 to 50 μm, the thickness of the R2 layer is 1 to 10 μm, and the thickness ratio R1 / R2 between the R1 layer and the R2 layer is R1 / R2 = 1/1 to 20/1. The resin film for metal plate lamination according to claim 12, wherein A polyester resin layer mainly composed of polyethylene terephthalate copolymerized with polyethylene terephthalate and / or isophthalic acid on one surface of the resin layer R1 layer made of the mixed resin according to any one of claims 1 to 8. R0 layer / R1 layer / R0 layer is laminated, and a resin layer R2 layer mainly composed of a modified polyolefin resin having a functional group derived from carboxylic acid is laminated on the other surface of the R1 layer. A resin film for laminating a metal plate, which is a film having a three-layer structure of R2 layers and designed so that the R0 layer becomes an outermost layer when laminated on a metal plate. The film thickness of the R1 layer is 10 to 50 μm, the film thickness of the R0 layer is 1 to 10 μm, the film thickness of the R2 layer is 1 to 10 μm, and the thickness ratio R1 / R0 between the R1 layer and the R0 layer is R1 / R0. The metal plate laminate according to claim 14, wherein R0 = 2/1 to 10/1 and a thickness ratio R1 / R2 to the R2 layer is R1 / R2 = 1/1 to 20/1. Resin film. The metal according to any one of claims 12 to 15, wherein the modified polyolefin resin of the R2 layer contains a functional group derived from carboxylic acid in a weight ratio of 2 to 20% by weight in terms of carboxylic acid. Resin film for laminate. The resin film for metal plate lamination according to any one of claims 10 to 16, wherein the resin film contains a pigment in an amount of 5 to 40% by weight. In producing the resin film for metal plate lamination according to any one of claims 1 to 9, the particle diameter of the thermoplastic polyester resin according to any one of claims 1 to 8 as a raw material resin A method for producing a resin film for laminating a metal plate, comprising: mixing a resin in which a granular modified polyolefin resin having a particle size of 0.1 to 5 μm is dispersed in advance into an extruder and melting the resin, and forming an extruded film from a T die. In producing the resin film for laminating a metal plate according to claim 10, 11 or 17, the thermoplastic polyester resin according to any one of claims 1 to 8 is used as a raw material for the R1 layer. A mixed resin in which a granular modified polyolefin resin having a particle size of 0.1 to 5 μm is dispersed in advance is inserted into an extruder and melted. At the same time, polyethylene terephthalate and / or isophthalic acid is used as a resin as a raw material for the R0 layer. A polyester resin having a copolymerized polyethylene terephthalate as the main basic skeleton is inserted into another extruder and melted. The molten resin is extruded from one T die and formed into a film having a two-layer structure of R1 layer / R0 layer. The manufacturing method of the resin film for metal plate lamination characterized by the above-mentioned. The thermoplastic polyester according to any one of claims 1 to 8, as a resin used as a raw material for the R1 layer in producing the resin film for metal plate lamination according to claim 12, 13, 16 or 17. A mixed resin in which a granular modified polyolefin resin having a particle diameter of 0.1 to 5 μm in the resin is dispersed in advance is inserted into an extruder and melted, and at the same time, derived from carboxylic acid as a resin to be a raw material of the R2 layer. A resin having a modified polyolefin resin having a functional group as a main component is inserted into another extruder and melted, and the molten resin is extruded from one T-die to form a film having a two-layer structure of R1 layer / R2 layer. The manufacturing method of the resin film for metal plate lamination characterized by the above-mentioned. In producing the resin film for metal plate lamination according to claim 14 to 17, as a resin that is a raw material of the R1 layer, particles in the thermoplastic polyester resin according to any one of claims 1 to 8 are used. A mixed resin in which a granular modified polyolefin resin having a diameter of 0.1 to 5 μm is dispersed in advance is inserted into an extruder and melted. At the same time, polyethylene terephthalate and / or isophthalic acid is used as a resin for the R0 layer. Extruders each having a polyester resin mainly composed of polymerized polyethylene terephthalate and a resin mainly composed of a modified polyolefin resin having a functional group derived from a carboxylic acid as a raw material for the R2 layer Insert into a different extruder and melt and extrude the molten resin from one T-die , Metal plate manufacturing method of laminating a resin film, which comprises forming a film of three-layer structure of R0 layer / R1 layer / R2 layer. The resin film described in any one of claims 1 to 17 or the resin film manufactured by the method described in any one of claims 18 to 21 is coated on at least one surface of a metal plate. A laminated metal plate characterized by that. Metal plate, a metal layer of chromium coating weight 50-200 mg / ^{m 2} on the surface, and wherein the amount of adhesion of the metal chromium conversion is electrolytic chromate treated steel sheet having a chromium oxide layer of 3 to 30 mg / ^{m 2} The laminated metal plate according to claim 22. The laminated metal plate according to claim 22 or 23, wherein a plane orientation coefficient in a direction parallel to the film surface of the resin film is less than 0.010. The said resin film is what was coated by the extrusion laminating method by which the mixed resin as described in any one of Claims 1-8 is extruded from T-die, and is directly coat | covered on the metal plate surface, It is characterized by the above-mentioned. The laminated metal plate according to any one of claims 22 to 24. The resin film is mainly composed of a resin layer (R1 layer) made of the mixed resin according to any one of claims 1 to 8, and polyethylene terephthalate copolymerized with polyethylene terephthalate and / or isophthalic acid. It is characterized in that two types of resins consisting of a resin layer (R0 layer) consisting of a polyester resin are coated by a two-layer extrusion laminating method in which a resin is simultaneously extruded from one T die and directly coated on the surface of a metal plate. The laminated metal plate according to any one of claims 22 to 24. The resin film is a resin mainly composed of a resin layer (R1 layer) composed of the mixed resin according to any one of claims 1 to 8 and a modified polyolefin resin having a functional group derived from carboxylic acid. 25. The resin according to claim 22, wherein two kinds of resins comprising the layer R2 are coated by a two-layer extrusion laminating method in which the resin is simultaneously extruded from one T die and directly coated on the surface of the metal plate. The laminated metal plate according to any one of the items. The resin film is described in any one of claims 1 to 8 and a resin layer (R0 layer) made of a polyester resin having polyethylene terephthalate and / or polyethylene terephthalate copolymerized with isophthalic acid as a main basic skeleton. Three types of resin consisting of a resin layer (R1 layer) made of a mixed resin and a resin layer R2 layer mainly composed of a modified polyolefin resin having a functional group derived from carboxylic acid are extruded from one T die at the same time. The laminated metal plate according to any one of claims 22 to 24, which is coated by a three-layer extrusion lamination method in which the surface of the metal plate is directly coated. In producing the laminated metal plate according to any one of claims 22 to 28, the melting point of the polyester resin in the mixed resin according to any one of claims 1 to 8-70 ° C to the melting point + 30 ° C. A method for producing a laminated metal plate, comprising laminating a resin film on a metal plate heated to the above range. In manufacturing the laminated metal plate according to claim 25, the mixed resin is heated and melted in the range of the melting point of the polyester resin in the mixed resin + 10 ° C to the melting point + 50 ° C, and then directly on the surface of the metal plate. A method for producing a laminated metal plate, comprising extruding and laminating. As a raw material resin, a mixed resin in which a granular modified polyolefin resin having a particle size of 0.1 to 5 μm is dispersed in advance in the thermoplastic polyester resin described in any one of claims 1 to 8 is extruded. The method for producing a laminated metal plate according to claim 30, wherein the laminated metal plate is extruded and laminated directly on the surface of the metal plate after being inserted into a machine and melted. 27. In manufacturing the laminated metal plate according to claim 26, the R1 layer and the R0 layer are heated in the range of the melting point of the polyester resin of the R1 layer + 10 ° C. to the melting point + 50 ° C. A method for producing a laminated metal sheet, characterized in that two layers are extruded and laminated. A mixture in which a granular modified polyolefin resin having a particle diameter of 0.1 to 5 μm is dispersed in advance in the thermoplastic polyester resin described in any one of claims 1 to 8 as a resin as a raw material of the R1 layer The resin is inserted into an extruder, and at the same time, as the raw material for the R0 layer, a resin composed of a polyester resin mainly composed of polyethylene terephthalate and / or polyethylene terephthalate copolymerized with isophthalic acid is inserted into another extruder. The method for producing a laminated metal plate according to claim 32, wherein after melting them, they are directly extruded onto the surface of the metal plate and laminated. In manufacturing the laminated metal plate according to claim 27, the R1 layer and the R2 layer are heated to a melting point of the polyester resin of the R1 layer in the range of + 10 ° C to the melting point + 50 ° C and melted, and then the surface of the metal plate A method for producing a laminated metal sheet, characterized in that two layers are extruded and laminated. A mixture in which a granular modified polyolefin resin having a particle diameter of 0.1 to 5 μm is dispersed in advance in the thermoplastic polyester resin described in any one of claims 1 to 8 as a resin as a raw material of the R1 layer The resin is inserted into an extruder, and at the same time, as the resin used as the raw material for the R2 layer, a resin mainly composed of a modified polyolefin resin having a functional group derived from carboxylic acid is inserted into another extruder and melted. 35. The method of manufacturing a laminated metal plate according to claim 34, wherein the laminate is directly extruded on the surface of the metal plate and laminated. In manufacturing the laminated metal plate according to claim 28, the R1 layer, the R2 layer, and the R0 layer are heated to a melting point of the polyester resin of the R1 layer in a range of + 10 ° C to a melting point + 50 ° C, and then melted. A method for producing a laminated metal plate, characterized in that three-layer extrusion lamination is performed on the surface of the plate. A mixture in which a granular modified polyolefin resin having a particle diameter of 0.1 to 5 μm is dispersed in advance in the thermoplastic polyester resin described in any one of claims 1 to 8 as a resin as a raw material of the R1 layer Resin is inserted into an extruder and melted, and at the same time, a resin composed of a polyester resin mainly composed of polyethylene terephthalate copolymerized with polyethylene terephthalate and / or isophthalic acid is used as a raw material for the R0 layer. As a resin used as a raw material, a resin containing a modified polyolefin resin having a functional group derived from a carboxylic acid as a main component is inserted into an extruder different from each of the extruders, and after melting them, a metal The laminate metal plate according to claim 36, wherein the laminate metal plate is extruded and laminated directly on the surface of the plate. Production method.